WO2015134256A1

WO2015134256A1 - Combinatorial libraries

Info

Publication number: WO2015134256A1
Application number: PCT/US2015/017659
Authority: WO
Inventors: Vincent FRANCO; Zheng-zheng HUANG; Anilkumar Raghavanpillai; Subramaniam Sabesan
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2014-02-28
Filing date: 2015-02-26
Publication date: 2015-09-11

Abstract

Synthetic mixtures comprising two or more synthetic oligoglucosamine based derivatives have been found to be useful in agricultural compositions for promoting seed germination. The disclosed synthetic mixtures may be applied to plant propagating materials, including seeds and other regenerable plant parts, including cuttings, bulbs, rhizomes and tubers. They may also be applied to foliage, or soil either prior to or following planting of plant propagating materials. Such applications may be made alone or in combination with fungicides, insecticides, nematicides and other agricultural agents used to improve plant growth and crop yield.

Description

TITLE

Combinatorial Libraries

FIELD OF THE DISCLOSURE

[01] The present disclosure is directed toward compositions comprising two or more synthetic compounds that are useful for improving plant growth and crop yield.

BACKGROUND OF DISCLOSURE

[02] There is a need for cost-effective synthetically-produced

compounds that improve plant health and result in improved plant growth and crop yield. The present disclosure addresses this need.

SUMMARY OF THE DISCLOSURE

[03] The present disclosure is directed towards a synthetic mixture comprising two or more compounds, wherein each of the compounds comprise a non-reducing glucose unit, a reducing glucose unit and at least one substituent -AR²; wherein the at least two or more compounds are; a. a compound having a structure (1 -1 ), wherein the at least one substituent -AR² is at the non-reducin glucose unit:

(1 -1 ).

b. a compound having a structure (1 -2), wherein the at least one substituent -AR² is at the reducin glucose unit:

c. a compound having a structure (1 -3), wherein the at least one substituent -AR² is at a glucose unit penultimate to the non- reducin glucose unit:

(1 -3), or

d. a compound having a structure (1 -4), wherein the at least one substituent -AR² is at a glucose unit penultimate to the reducing lucose unit:

(1 -4),

wherein m = 0 or 1 ; n = 0 or 1 ;

A is -C(O)-, -C(S)-, -C(S)NH-, -C(O)NH-, -C(O)O- or C(O)S-;

each Y¹ is independently H, -AR¹ or -AR²;

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

each R² is independently Ci₂ to C₂2 alkyl, Ci₂ to C₂2 alkenyl, Ci₂ to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

XR³ is an azide; or X is O or S and R³ is H, Ci to Ce alkyl or aryl; each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C2 to C12 alkenylene or C2 to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R1 )- or -NHC(O)-;

each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C2 to C12 alkenyl, or C2 to C12 alkynyl;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹ )₂, -C_qF_2q+i , -OC_qF_2q+i , -NO2, -N₃, -OR¹ , SR¹ , N(R¹ )₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl; and wherein structures (1 -1 ), (1 -2), (1 -3) and (1 -4) are different from each other.

[04] The present disclosure also relates to a process comprising;

1 ) providing one or more compounds having a structure according to A B and/or C in a liquid carrier;

2) contacting the one or more compounds A, B and/or C with an

acylating agent having a formula:

wherein XR³ is an azide; or X is O or S and R³ is H, Ci to C₆ alkyl or aryl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to C22 alkynyl or -R⁴-R⁵-R⁶;

each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C2 to C12 alkenylene or C2 to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-; each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C2 to C12 alkenyl, or C2 to C12 alkynyl; each R⁴ and R⁶ is optionally substituted by 1 to 2

substituents chosen independently from halogen, -CN, -C(O)OR¹, -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO₂, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6; each R¹ is independently H, Ci to C6 alkyl, aryl, or aralkyl; G is O or S; and

Z is -OH, halogen, methoxy or ethoxy;

in the presence of a base or a carboxylic acid activator; and 3) optionally acylating any remaining amines with a second acylating agent; or optionally contacting any remaining amines with a Ci to C6 isocyanate.

[05] In other embodiments of the process, the acylating agent of step 2) is an acid halide.

[06] In other embodiments of the process, the second acylating agent is acetic anhydride.

[07] In other embodiments of the process, the acid halide is palmitoleic acid chloride.

[08] In other embodiments of the process, the ratio of the number of maoles of acylating agent to the number of moles of amine in the one or more compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 .

[09] The present disclosure also relates to a process comprising;

2) contacting the one or more compounds A, B and/or C with an

acylating agent having a formula:

R²-NCG wherein XR³ is an azide; or X is O or S and R³ is H, Ci to C6 alkyl or aryl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-; each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C₂ to C12 alkenyl, or C₂ to C12 alkynyl;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO₂, -N_3> -OR¹ , SR¹ , N(R¹ )₂, and Ci to C₆ alkyl; q is 1 to 6; each R¹ is independently H, Ci to C6 alkyl, aryl, or aralkyl; G is O or S; and

3) optionally acylating any remaining amines with a second acylating agent; or optionally contacting any remaining amines with a Ci to C6 isocyanate.

[10] The present disclosure also relates to an agricultural composition comprising an aqueous solution of the synthetic mixture.

[11] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"3 moles/liter (M) to 10^"12M.

[12] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"4 moles/liter (M) to 10^"5M.

[13] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"5 moles/liter (M) to 10^"6M.

[14] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"6 moles/liter (M) to 10^"7M.

[15] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"7 moles/liter (M) to 10^"8M. [16] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"8 moles/liter (M) to 10^"9M.

[17] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"9 moles/liter (M) to 10^"10M.

[18] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"10 moles/liter (M) to 10^{"1 1}M.

[19] In some embodiments, the synthetic mixture is present in the agricultural composition in the range of from 10^"11 moles/liter (M) to 10^"12M.

[20] In other embodiments, the agricultural composition further comprises insecticides, fungicides, nematicides, bactericides, acaricides, entomopathogenic bacteria, viruses, fungi, microorganisms, growth regulators, signal compounds or a combination thereof.

[21] In other embodiments, the growth regulator is selected from rooting stimulants, chemosterilants, repellents, attractants, pheromones, feeding stimulants or a combination thereof.

[22] In other embodiments, the signal compound is apocarotenoids, flavonoids, jasmonates, strigolactones or a combination thereof.

[23] In other embodiments, the signal molecule is a

lipochitooligosaccharide.

[24] In other embodiments, the agricultural composition is applied to propagating material of a plant.

[25] In other embodiments, the propagating material is a seed.

[26] In other embodiments, the agricultural composition is applied to the seed as a seed coating to increase rate of germination, seedling

emergence, radicle growth, early growth, plant height, vigor, plant health, biomass and/or yield.

[27] In other embodiments, the present disclosure relates to a method of treating a propagule comprising the steps of

a) providing the aforementioned agricultural composition; and b) contacting the propagule with the agricultural composition.

[28] In other embodiments, the propagule is a seed, thereby forming a seed coating. [29] In other embodiments, the plant seed is coated by the agricultural composition and the agricultural composition further comprises an insecticide, a fungicide, a nematicide and a biological agent.

[30] In other embodiments, the present disclosure relates to a plant seed coated by the agricultural composition.

[31] In other embodiments, the plant seed is coated by the agricultural composition and the agricultural composition further comprises an insecticide, a fungicide, a nematicide and a biological agent.

[32] In other embodiments, the resulting plant expresses an insect resistant trait.

[33] In other embodiments, the insect resistant trait is due to the expression of a Bt protein.

[34] In other embodiments, the step of contacting the propagule with the agricultural composition comprises contacting the propagule with the agricultural composition through application of the agricultural composition to soil either prior to or following planting the propagule.

[35] Also included in this disclosure are processes for preparing the synthetic mixtures, synthetic mixture formed by the processes, agricultural compositions comprising the synthetic mixture and methods of treating plant material using the agricultural compositions.

DETAILED DESCRIPTION

[36] The features and advantages of the present disclosure will be more readily understood, by those of ordinary skill in the art from reading the following detailed description. It is to be appreciated that certain features of the disclosure, which are, for clarity, described above and below in the context of separate embodiments, may also be provided in combination in a single element. Conversely, various features of the disclosure that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. In addition, references to the singular may also include the plural (for example, "a" and "an" may refer to one or more) unless the context specifically states otherwise.

[37] The use of numerical values in the various ranges specified in this application, unless expressly indicated otherwise, are stated as approximations as though the minimum and maximum values within the stated ranges were both proceeded by the word "about". In this manner, slight variations above and below the stated ranges can be used to achieve substantially the same results as values within the ranges. Also, the disclosure of these ranges is intended as a continuous range including each and every value between the minimum and maximum values.

[38] As used herein:

[39] The phrase "reducing glucose unit" refers to a terminal glucose ring wherein the carbon atom that is located at the 1 - position of the ring is - CH(XR³).

[40] The phrase "non-reducing glucose unit" refers to a terminal glucose ring wherein the carbon atom that is located at the 3- and 4- positions on the ring are both -CH(OH)-.

[41] The term "agricultural composition" as used herein refers to one or more substances formulated for at least one agricultural application.

Agricultural applications are any application that enhances plant performance, such as, for example, plant health, germination

improvement, growth improvement, yield improvement, pest control, disease control and resistance to abiotic environmental stress.

[42] As used herein the term "biologically effective amount" refers to that amount of a substance required to produce the desired effect on a plant, plant propagating material and/or plant part, such as, for example, germination improvement, growth improvement, yield improvement, pest control, disease control and resistance to abiotic environmental stress. Effective amounts of the composition will depend on several factors, including treatment method, plant species, propagating material type and environmental conditions.

[43] Foliage as defined in the present application includes all aerial plant organs, for example, the leaves, stems, flowers and fruit.

[44] As used herein, "percent germination" refers the percentage of seeds that germinate after planting or being placed under conditions otherwise suitable for germination. The term "accelerate the rate of germination" and its equivalents refer to an increase in the percent germination of experimentally treated seeds compared to seeds

designated as experimental controls as a function of time. In the

Examples presented herein, seed germination rates were determined with laboratory-based germination assays conducted under optimum conditions for germination wherein germination percentages were determined at a specified time following initiation of the experiment. General descriptions of seed germination tests can be found in the Handbook of Seed

Technology for Genebanks, Volume I. Principles and Methodology, R.H. Ellis, T.D. Hong and E.H. Roberts, Eds., International Board for Plant Genetic resources, Rome, 1985, pp. 94-120 and the Seed Vigor Testing Handbook, Contribution No. 32 to the Handbook on Seed Testing prepared by the Seed Vigor Test Committee of the Association of Official Seed Analysts, 1983. Examples of seed cold and salt stress germination assays are respectively described in Burris and Navratil, Agronomy Journal, 71 : 985-988 (1979) and Scialabba, et al., Seed Science &

Technology, 27: 865-870 (1999).

[45] The term "plant growth" as used herein is defined by, but not limited to, measurements of seedling emergence, standability, radicle growth, early growth, plant height, time to flowering, tillering (for grasses), days to maturity, vigor, biomass and yield.

[46] The term "propagating material" as used herein means a seed or regenerable plant part. The term "regenerate plant part" means a part of the plant other than a seed from which a whole plant may be grown or regenerated when the plant part is placed in agricultural or horticultural growing media such as moistened soil, peat moss, sand, vermiculite, perlite, rock wool, fiberglass, coconut husk fiber, tree fern fiber, or even a completely liquid medium such as water. Regenerable plant parts commonly include rhizomes, tubers, bulbs and corms of such geophytic plant species as potato, sweet potato, yam, onion, dahlia, tulip, narcissus, etc. Regenerable plant parts include plant parts that are divided (e.g., cut) to preserve their ability to grow into a new plant. Therefore regenerable plant parts include viable divisions of rhizomes, tubers, bulbs and corms which retain meristematic tissue, such as an eye. Regenerable plant parts can also include other plant parts such as cut or separated stems and leaves from which some species of plants can be grown using horticultural or agricultural growing media. As referred to in the present disclosure and claims, unless otherwise indicated, the term "seed" includes both unsprouted seeds and seeds in which the testa (seed coat) still surrounds part of the emerging shoot and root.

[47] The term "rhizosphere" as used herein refers to the area of soil that immediately surrounds and is affected by the plant's roots.

[48] The term "treating" as used herein means applying a biologically effective amount of a plant performance enhancing compound, or a composition containing the compound, to a seed or other plant

propagating material, plant foliage or plant rhizosphere; related terms such as "treatment" are intended to be interpreted analogously.

[49] The term "yield" as defined herein refers to the return of crop material per unit area obtained after harvesting a plant crop. An increase in crop yield refers to an increase in crop yield relative to an untreated control treatment. Crop materials include, but are not limited to, seeds, fruits, roots, tubers, leaves and types of crop biomass. Descriptions of field-plot techniques used to evaluate crop yield may be found in W.R. Fehr, Principles of Cultivar Development, McGraw-Hill, Inc., New York, NY, 1987, pp. 261 -286 and references incorporated therein.

[50] "Insect resistant trait" is used herein to refer to a plant containing a toxin that has toxic acitivity against one or more pests, including, but not limited to, members of the Lepidoptera, Diptera, Hemiptera and

Coleoptera orders or the Nematoda phylum or a protein that has homology to such a protein. Pesticidal proteins have been purified from organisms including, for example, Bacillus sp., Pseudomonas sp., Photorhabdus sp., Xenorhabdus sp., Clostridium bifermentans and Paenibacillus popilliae. Pesticidal proteins include but are not limited to: insecticidal proteins from Pseudomonas sp. such as PSEEN3174 (Monalysin; (201 1 ) PLoS

Pathogens 7:1 -13); from Pseudomonas protegens strain CHAO and Pf-5 (previously fluorescens) (Pechy-Tarr, (2008) Environmental Microbiology 10:2368-2386; GenBank Accession No. EU400157); from Pseudomonas Taiwanensis (Liu, et al., (2010) J. Agric. Food Chem., 58:12343-12349) and from Pseudomonas pseudoalcligenes (Zhang, et al., (2009) Annals of Microbiology 59:45-50 and Li, et al., (2007) Plant Cell Tiss. Organ Cult. 89:159-168); insecticidal proteins from Photorhabdus sp. and

Xenorhabdus sp. (Hinchliffe, et al., (2010) The Open Toxicology Journal, 3:101 -1 18 and Morgan, et al., (2001 ) Applied and Envir. Micro. 67:2062- 2069); US Patent Number 6,048,838, and US Patent Number 6,379,946; a PIP-1 polypeptide of US Patent Publication US20140007292; an AflP-1A and/or AflP-1 B polypeptide of US Patent Publication US20140033361 ; a PHI-4 polypeptide of US patent Publication US20140274885 and PCT Patent Publication WO2014/150914; a PIP-47 polypeptide of PCT Serial Number PCT/US14/51063, a PIP-72 polypeptide of PCT Serial Number PCT/US14/55128, and δ-endotoxins including, but not limited to, the Cry1 , Cry2, Cry3, Cry4, Cry5, Cry6, Cry7, Cry8, Cry9, Cry10, Cry1 1 , Cry12, Cry13, Cry14, Cry15, Cry16, Cry17, Cry18, Cry19, Cry20, Cry21 , Cry22, Cry23, Cry24, Cry25, Cry26, Cry27, Cry 28, Cry 29, Cry 30, Cry31 , Cry32, Cry33, Cry34, Cry35,Cry36, Cry37, Cry38, Cry39, Cry40, Cry41 , Cry42, Cry43, Cry44, Cry45, Cry 46, Cry47, Cry49, Cry50, Cry51 , Cry52, Cry53, Cry 54, Cry55, Cry56, Cry57, Cry58, Cry59, Cry60, Cry61 , Cry62, Cry63, Cry64, Cry65, Cry66, Cry67, Cry68, Cry69, Cry70, Cry71 , and Cry 72 classes of δ-endotoxin genes and the B. thuringiensis (Bt) cytolytic cytl and cyt2 genes.

[51] The term "alkyl" means a linear or branched alkyl. Suitable examples of such alkyl groups can include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, isobutyl, pentyl, neopentyl, hexyl, heptyl, isoheptyl,

2-ethylhexyl, cyclohexyl and octyl. The term "alkylene" means linear or branched alkanediyl. Suitable examples include CH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃) and the different butylene isomers. The terms

"C/ to C alkyl" or "C, to C, alkylene" means that the alkyl or alkylene group contains in the range of from i to j carbon atoms, for example, Ci to C₆ alkyl means an alkyl group having from 1 to 6 carbon atoms.

[52] The term "alkenyl" means a monovalent linear or branched alkene containing at least one carbon-carbon double bond. Suitable examples of alkenyl groups can include CH=CH₂, CH₂CH=CH₂, CH=CH(CH₃). The term "alkenylene" denotes a linear or branched alkenediyl containing at least one carbon-carbon double bond. Examples of "alkenylene" include CH=CH, C=CH₂, CH₂CH=CH, CH=C(CH₃) and the various butenylene isomers. The terms "C, to C alkenyl" or "C, to C alkenylene" means an alkenyl or alkenylene group having in the range of from i to j carbon atoms, for example, C₂ to Ce alkenyl means an alkenyl group having from 2 to 6 carbon atoms. Each of the double bonds can be present in the cis and/or trans isomers.

[53] The term "alkynyl" means a monovalent linear or branched alkyne containing at least one carbon-carbon triple bond. Suitable examples of alkynyl groups can include C≡CH, CH₂C≡CH, C≡CCH₃, CH₂C≡CCH₃. The term "alkynylene" denotes a divalent linear or branched alkynediyl containing at least one carbon-carbon triple bond. Examples of

"alkynylene" include C≡C, CH₂C≡CCH₂, CH₂C≡C and the various butynylene isomers. The terms "C, to C, alkynyl" or "C, to C, alkynylene" means an alkynyl or alkynylene group having in the range of from i to j carbon atoms, for example, C₂ to Ce alkynyl means an alkynyl group having from 2 to 6 carbon atoms.

[54] The term "aryl" is known in the art to mean a group defined as a monovalent radical formed conceptually by removal of a hydrogen atom from a hydrocarbon that is structurally composed of one or more benzene rings. Common examples of such hydrocarbons include benzene, biphenyl, terphenyl, naphthalene, phenyl naphthalene, and

naphthylbenzene. Aryl groups, as used herein, include aromatic

carbocyclic groups having a single ring, multiple rings or multiple fused rings in which at least one is aromatic, for example, phenyl, biphenyl, 1 ,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl. The aryl group can optionally be mono- or di-substituted with, halogen, -CN, -C(O)OR¹, -C(O)N(R¹)₂, -C_qF_2q+1 , -OC_qF_2q+1 , -NO₂, -N₃, -OR¹ , SR¹, N(R¹)₂, and Ci to C6 alkyl; q is 1 to 6.

[55] The term "arylene" is known in the art to mean a group defined as a divalent radical formed conceptually by removal of two hydrogen atoms from a hydrocarbon that is structurally composed of one or more benzene rings. Common examples of such hydrocarbons include benzene, biphenyl, terphenyl, naphthalene, phenyl naphthalene, and

naphthylbenzene. Arylene groups, as used herein, include aromatic carbocyclic groups having a single ring, multiple rings or multiple fused rings in which at least one is aromatic, for example, phenylene,

biphenylene, 1 ,2,3,4-tetrahydronaphthylene, naphthylene, anthrylene, or phenanthrylene. The arylene group can optionally be mono- or

di-substituted with, halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO2, -N₃, -OR¹, SR¹, N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6.

[56] The term "heteroaryl" is defined as a monovalent 5- or 6-membered aromatic ring systems having in the range of from 1 to 3 hetero atoms wherein the heteroatoms are nitrogen, oxygen and/or sulfur. Heteroaryl groups containing fused rings are also included provided that at least one ring contains at least one heteroatom. Examples of suitable heteroaryl groups can include, for example, pyridyl, pyrimidinyl, pyrrolyl, pyrazolyl, pyrazinyl, pyridazinyl, oxazolyl, furanyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, benzothienyl, thiazolyl, and thienyl. The heteroaryl group can optionally be mono- or di-substituted with, halogen, -CN, -C(O)OR¹, -C(O)N(R¹)₂, -C_qF_2q+1 , -OC_qF_2q+1, -NO₂, -N₃, -OR¹, SR¹, N(R¹)₂, and d to C6 alkyl; q is 1 to 6. The point of attachment can be through any carbon or available nitrogen atom by replacement of hydrogen on the carbon or nitrogen atom.

[57] The term "heteroarylene" is defined as divalent 5- or 6-membered aromatic ring systems having in the range of from 1 to 3 hetero atoms wherein the heteroatoms are nitrogen, oxygen and/or sulfur. Heteroaryl groups containing fused rings are also included provided that at least one ring contains at least one heteroatom. Examples of heteroaryl groups that can be used for the heteroarylene include, pyridyl, pyrimidinyl, pyrrolyl, pyrazolyl, pyrazinyl, pyridazinyl, oxazolyl, furanyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, benzothienyl, thiazolyl, and thienyl. The heteroarylene group can optionally be mono- or di-substituted with, halogen, -CN, -C(O)OR¹, -C(O)N(R¹)₂, -C_qF_2q+1 , -OC_qF_2q+1 , -NO₂, -N₃, -OR¹ , SR¹, N(R¹)₂, and Ci to C6 alkyl; q is 1 to 6. The point of attachment can be through any carbon or available nitrogen atom by replacement of hydrogen on the carbon or nitrogen atom.

[58] In an effort to produce new synthetic mixtures that have enhanced activity when used as in an agricultural composition, a process has been developed to create synthetic mixtures comprising two or more synthetic compounds. Naturally occurring lipo-oligosaccharides have a backbone of two to four β 1 ,4-linked N-acylated glucosamine residues wherein a single fatty acid chain is exclusively located at the terminal non-reducing glucose unit. Non-naturally occurring synthetic compounds are substituted with - AR² at the reducing glucose unit and/or substituted with -AR² at one or more of the nitrogen atoms of the non-terminal glucose units. In the case of synthetic compounds that have only two rings, the substituent -AR² is present on the nitrogen atom of the reducing glucose unit or on the nitrogen atoms of both rings. In some embodiments, the disclosed synthetic mixtures contain naturally occurring lipo-oligosaccharides compounds; in other embodiments, the synthetic mixtures contain synthetic compounds that do not occur in nature; and in still further embodiments, the synthetic mixtures contain both naturally occurring lipo- oligosaccharides compounds and non-naturally occurring synthetic compounds.

[59] In one embodiment, the disclosure is related to a process comprising;

1 ) providing one or more compounds having a structure accordin to A, B and/or C in a liquid carrier;

2) contacting the one or more compounds A, B and/or C with an acylating agent having a formula:

wherein XR³ is an azide; or X is O or S and R³ is H, Ci to C6 alkyl or aryl;

each R² is independently C12 to C22 alkyl. C12 to C22 alkenyl, C12 to C22 alkynyl or -R⁴-R⁵-R⁶;

each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C₂ to C12

alkenylene or C2 to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-; each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C2 to C12 alkenyl, or C2 to C12 alkynyl;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO₂, -N₃, -OR¹ , SR¹ , N(R¹ )₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl; G is O or S; and

Z is -OH, halogen, methoxy or ethoxy;

in the presence of a base or a carboxylic acid activator; and

3) optionally acylating any remaining amines with a second acylating agent; or optionally contacting any remaining amines with a Ci to Ce isocyanate.

[60] In another embodiment, the acylating agent of step 2) is an acid halide.

[61] In a further embodiment, the second acylating agent is acetic anhydride. [62] In a further embodiment of the above process, the acid halide is palmitoleic acid chloride.

[63] In another embodiment, the ratio of the number of moles of the acylating agent to the number of moles of amine in the one or more compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 .

[64] Another embodiment of the present disclosure is a synthetic mixture formed by the above described process.

[65] In another embodiment, the process comprises;

1 ) providing one or more compounds having a structure

accordin to A, B and/or C in a liquid carrier;

2) contacting the one or more compounds A, B and/or C with an isocyanate functional compound having a formula;

R²-NCG

wherein XR³ is an azide; or X is O or S and R³ is H, Ci to Ce alkyl or aryl;

each R² is independently Ci₂ to C₂2 alkyl, Ci₂ to C₂2 alkenyl, Ci₂ to C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C₂ to C12 alkenylene or C₂ to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C2 to C12 alkenyl, or C2 to C12 alkynyl; each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i, -OC_qF_2q+i , -NO₂, -N₃, -OR¹ , SR¹, N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to C6 alkyl, aryl, or aralkyl;

G is O or S; and wherein the ratio of the number of moles of the isocyanate functional compound R²-NCG to the number of moles of amine in the one or more compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 ;

3) optionally contacting any remaining amine with a second acylating agent; or optionally contacting any remaining amines with a Ci to C₆ isocyanate compound.

[66] In another embodiment, the second acylating agent is acetic anhydride.

[67] In still another embodiment, the ratio of the number of moles of isocyanate to the number of moles of amine in the one or more

compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 .

[68] In still further embodiments, the disclosure relates to a

synthetic mixture comprising two or more compounds, wherein each of the two or more compounds comprises a non-reducing glucose unit, a reducing glucose unit, and at least one N-linked substituent -AR²:

a. a compound having a structure (1 -1 ), wherein the at least one N-linked substituent -AR² is at the non-reducin glucose unit:

(1 -1 ).

b. a compound having a structure (1 -2), wherein the at least one N-linked substituent -AR² is at the reducing glucose unit:

(1 -2),

c. a compound having a structure (1 -3), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the non-reducin glucose unit:

(1 -3), or

d. a compound having a structure (1 -4), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the reducin glucose unit:

(1 -4),

wherein m = 0 or 1 ; n = 0 or 1 ;

A is -C(O)-, -C(S)-, -C(S)NH-, -C(O)NH-, -C(O)O- or C(O)S-;

each Y¹ is independently H, -AR¹ or -AR²;

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

XR³ is an azide; or X is O or S and R³ is H, Ci to C₆ alkyl or aryl; each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C2 to C12 alkenylene or C2 to C12 alkynylene;

each R¹ is independently H, Ci to C₆ alkyl, aryl, or aralkyl; and wherein structures (1 -1 ), (1 -2), (1 -3) and (1 -4) are different from each other.

[69] In another embodiment of the synthetic mixture disclosed above, are mixtures wherein m=0 and n=0, comprising:

a. a compound having a structure (2-1 ), wherein the at least one N-linked substituent -AR² is at the non-reducin glucose unit:

(2-1 ), and

b. a compound having a structure (2-2), wherein the at least one N-linked substituent -AR² is at the reducin glucose unit:

(2-2)

A is -C(O)-, -C(S)-, -C(S)NH-, -C(O)NH-, -C(O)O- or C(O)S-; each Y¹ is independently H, -AR¹ or -AR²;

each R¹ is independently H, Ci to C6 alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

XR³ is azide; or X is O or S and R³ is H, Ci to C₆ alkyl or aryl; each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C₁₂ alkylene, C2 to C12 alkenylene or C2 to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C₁₂ alkyl, C₂ to C₁₂ alkenyl, or C₂ to C₁₂ alkynyl;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i, -OC_qF_2q+i , -NO2, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to C₆ alkyl, aryl, or aralkyl; and wherein the structures (2-1 ) and (2-2) are different from each other.

[70] In still further embodiments, m=1 and n=0, comprising two or more of:

a. a compound having a structure (3-1 ), wherein the at least one N-linked substituent -AR² is at the non-reducin glucose unit:

(3-1 )

b. a compound having a structure (3-2), wherein the at least one N-linked substituent -AR² is at the reducin glucose unit:

(3-2), or

c. a compound having a structure (3-3), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the reducing or the non-reducing glucose unit:

(3-3), and

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

XR³ is azide; or X is O or S and R³ is H, Ci to C₆ alkyl or aryl; each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C2 to C12 alkenylene or C2 to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R¹ is independently H, Ci to C₆ alkyl, aryl, or aralkyl; and wherein the structures (3-1 ), (3-2) and (3-3) are different from each other.

[71] In still further embodiments, m=1 and n=1 , comprising two or more a. a compound having a structure (4-1 ), wherein the at least one N-linked substituent -AR² is at the non-reducin glucose unit:

(4-1 )

b. a compound having a structure (4-2), wherein the at least one N-linked substituent -AR² is at the reducin glucose unit:

(4-2)

c. a compound having a structure (4-3), wherein the at least one N-linked substituent -AR² is at the glucose unit penultimate to the non-reducin glucose unit:

(4-3), or

d. a compound having a structure (4-4), wherein the at least one N-linked substituent -AR² is at the glucose unit penultimate to the reducin glucose unit:

(4-4)

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

XR³ is azide; or X is O or S and R³ is H, Ci to C₆ alkyl or aryl; each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C₂ to C12 alkenylene or C₂ to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-; each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C₁₂ alkyl, C₂ to C₁₂ alkenyl, or C₂ to C₁₂ alkynyl;

each R¹ is independently H, Ci to C₆ alkyl, aryl, or aralkyl; and wherein the structures (4-1 ), (4-2), (4-3) and (4-4) are different from each other.

[72] In some embodiments, the desired synthetic mixture comprises two or more of the following synthetic compounds wherein each of compounds (1 -1 ), (1 -2), (1 -3) and (1 -4) comprises a reducing glucose unit, a non- reducing glucose unit, at least one N-linked substituent -AR² and the compounds (1 -1 ), (1 -2), (1 -3) and (1 -4) are different from one another; a. a compound having a structure (1 -1 ), wherein the at least one N-linked substituent -AR² is at the non-reducin glucose unit:

(1 -1 ).

b. a compound having a structure (1 -2), wherein the at least one N-linked substituent -AR² is at the reducin glucose unit:

(1 -2),

c. a compound having a structure (1 -3), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the non-reducing glucose unit:

(1 -3), or

(1 -4),

wherein m = 0 or 1 ; n = 0 or 1 ;

each R¹ is independently H, Ci to C₆ alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹ )₂, -C_qF_2q+i , -OC_qF_2q+i , -NO2, -N₃, -OR¹ , SR¹ , N(R¹ )₂, and Ci to C₆ alkyl; q is 1 to 6; and

wherein structures (1 -1 ), (1 -2), (1 -3) and (1 -4) are different from each other. In other embodiments, the synthetic mixture comprises;

a. a compound having a structure (2-1 ), wherein the at least one

N-linked substituent -AR² is at the non-reducin glucose unit:

(2-1 ), and

(2-2)

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

XR³ is an azide; or X is O or S and R³ is H, Ci to Ce alkyl or aryl; each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C₂ to C12 alkenylene or C₂ to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C₂ to C12 alkenyl, or C₂ to C12 alkynyl;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹ )₂, -C_qF_2q+i , -OC_qF_2q+i , -NO2, -N₃, -OR¹ , SR¹ , N(R¹ )₂, and Ci to C₆ alkyl; q is 1 to 6 ; and

wherein structures (2-1 ) and (2-2) are different from each other. [74] In other embodiments, the synthetic mixture comprises two or more of the following compounds;

(3-1 )

b. a compound having a structure (3-2), wherein the at least one N-linked substituent -AR² is at the reducing glucose unit:

(3-2), or

c. a compound having a structure (3-3), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the reducin or the non-reducing glucose unit:

(3-3), and

A is -C(O)-, -C(S)-, -C(S)NH-, -C(O)NH-, -C(O)O- or C(O)S-;

each Y¹ is independently H, -AR¹ or -AR²;

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

XR³ is an azide; or X is O or S and R³ is H, Ci to Ce alkyl or aryl; each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C₁₂ alkylene, C2 to C12 alkenylene or C2 to C12 alkynylene;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i, -OC_qF_2q+i , -NO2, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6 ; and\

wherein structures 3-1 , 3-2 and 3-3 are different from each other.

[75] In still further embodiments, the synthetic mixture comprises two or more of the following compounds;

a. a compound having the structure (4-1 ), wherein the at least one N-linked substituent -AR² is at the non-reducin glucose unit:

(4-1 )

b. a compound having the structure (4-2), wherein the at least one N-linked substituent -AR² is at a reducin glucose unit:

(4-2)

c. a compound having the structure (4-3), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the non-reducing glucose unit:

(4-3), or

d. a compound having the structure (4-4), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the reducin glucose unit:

(4-4)

A is -C(O)-, -C(S)-, -C(S)NH-, -C(O)NH-, -C(O)O- or C(O)S-;

each Y¹ is independently H, -AR¹ or -AR²;

each R¹ is independently H, Ci to C₆ alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

wherein structures 4-1 , 4-2, 4-3 and 4-4 are different from each other.

[76] In still further embodiments, the synthetic mixture comprises at least one of structure (1 -1 ) and at least one structure (1 -2). [77] The present disclosure also relates to an agricultural mixture comprising an aqueous solution of the above mentioned synthetic mixture.

[78] Another embodiment of the present disclosure also relates to agricultural compositions further comprising insecticides, fungicides, nematicides, bactericides, acaricides, entomopathogenic bacteria, viruses, fungi, microorganisms, growth regulators, signal compounds or a combination thereof.

[79] In still further embodiments, the growth regulators are selected from rooting stimulants, chemosterilants, repellents, attractants, pheromones, feeding stimulants or combinations thereof.

[80] In still further embodiments, the signal compound is selected from apocarotenoids, flavonoids, jasmonates, strigolactones or combinations thereof.

[81] The present disclosure also relates to a method of treating a propagule comprising steps:

a) providing the above agricultural composition; and

b) contacting the propagule with the agricultural composition.

[82] In further embodiments of the method of treating a propagule, the propagule is a seed thereby forming a seed coating.

[83] In further embodiments, step b) comprises contacting the propagule with the agricultural composition through application of the agricultural composition to soil either prior to or following planting the propagule.

[84] In still further embodiments of the method of treating the propagule, the agricultural composition can further comprise one or more of insecticides, fungicides, nematicides, bactericides, acaricides,

entomopathogenic bacteria, viruses, fungi, microorganisms, growth regulators, and signal compounds.

[85] In still further embodiments, the growth regulator is one or more of rooting stimulants, chemosterilants, repellents, attractants, pheromones, feeding stimulants, and combinations thereof. [86] And in still further embodiments, the signal compound one or more of apocarotenoids, flavonoids, jasmonates, strigolactones, and

combinations thereof.

[87] In still further embodiments, the synthetic mixture comprises two or more of the following compounds,

a. a compound having the structure (2-1 );

b. a compound having the structure (2-2);

c. a compound having the structure (3-1 );

d. a compound having the structure (3-2);

e. a compound having the structure (3-3);

f. a compound having the structure (4-1 );

g. a compound having the structure (4-2);

h. a compound having the structure (4-3); or

i. a compound having the structure (4-4), wherein each of said compounds (2-1 ), (2-2), (3-1 ), (3-2), (3-3), (4-1 ), (4-2), (4-3), and (4-4) are different from each other.

In still further embodiments, both of the terminal rings are substituted with the N-linked -AR², that is, the synthetic mixture comprises at least one of structure (1 -1 ) and one of structure (1 -2).

[88] In order to produce the desired synthetic mixtures containing two or more of the synthetic compounds, one or more intermediates dimer A, trimer B and tetramer C, are produced according to known methods. At least one suitable method for forming the intermediates A, B and C can be found in US Patent Number 7,485,718. In some embodiments, the intermediate dimer A, trimer B and tetramer D are produced as essentially pure compounds that do not contain any other oligoglucosamine products. For example, if it is desired to produce intermediate dimer A, then dimer A is produced and the desired intermediate product contains only

glucosamine-type structures having two glucosamine rings. Other non- glucosmaine reaction by products may be present, but the amount of oligoglucosamine products having 3, 4 or more glucosamine rings per molecule is less than 10 percent by weight or less than 5 percent by weight or less than 1 percent by weight, wherein all percentages by weight are based on the total amount of glucosamine product. The intermediate compounds are amine functional dimers, trimers or tetramers of

glucosamines having the following structures A, B and C:

[89] Another embodiment of the disclosure relates to a process comprising the steps of;

1 ) providing one or more compounds having a structure according to A, B and/or C in a liquid carrier;

2) contacting the one or more compounds A, B and/or C with an acylating agent having the formula:

wherein XR is an azide; or X is O or S and R is H, Ci to C6 alkyl or aryl;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO₂, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6; G is O or S; and

Z is -OH, halogen, methoxy or ethoxy;

in the presence of a base or a carboxylic acid activator; and

3) optionally acylating any remaining amines with a second acylating agent; or optionally contacting any remaining amines with a Ci to C₆ isocyanate.

[90] In some embodiments, the ratio of the number of moles of acylating agent to the number of moles of amine in the one or more compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 . In still further

embodiments, the process can comprise a further step 4) working up the mixture.

[91] Suitable acylating agents having the formula:

wherein R², G and Z defined as above. Acylating agents that are acid halides, carboxylic acid esters and carboxylic acid anhydrides may also be used. In some embodiments, the carboxylic acids have only one carboxylic group per molecule. In some embodiments, the acylating agent is an acid chloride and in a further embodiment the acid chloride is palmitoleic acid chloride. In some embodiments, the acylating agent can be a thioacylating agent of the formula R²-C(S)-Z, wherein the definitions of R² and Z are the same as those given above.

[92] According to the disclosed process, a suitable base can include, for example, tertiary amines, trialkyl amines, pyridine, 1 ,8-diazabicycloundec- 7-ene, Ν,Ν-diisopropylethylamine, triethylamine, sodium carbonate or sodium hydrogen carbonate. In general, strong bases, for example, sodium hydroxide, should not be used as the deprotonation of the hydroxyl groups of the one or more compounds A, B and/or C is not desired. As used herein, a "carboxylic activator" means a compound that is added to a mixture to promote the formation of an amide bond in the presence of a carboxylic acid and an amine. Suitable examples are known in the art and can include, for example, Ν,Ν'-dicyclohexylcarbodiimide and 1 -ethyl-3-(3- dimethylaminopropyl) carbodiimide.

[93] If any amines remain unreacted from step 1 ), the amines may optionally be acylated with a second acylating agent or contacted with a Ci to C6 isocyanate compound. Suitable second acylating agents can include, for example, carboxylic acids, or acid halides, esters, or anhydrides thereof. In one embodiment, the second acylating agent is acetic anhydride. Suitable isocyanate compounds can include, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, or hexyl isocyanate. Isomers of any of these may be used. The disclosure also relates to the products formed by the above mentioned process.

[94] In another embodiment, the process comprises the steps 1 ) and 3) above, and the step of 2) contacting the one or more structures according to A, B and/or C with an isocyanate functional compound having a structure according to R²-NCG, wherein R² and G are defined as above. In a further embodiment, the ratio of the number of moles of the

isocyanate functional compound R²-NCO to the number of moles of amine in the one or more compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 . In still further embodiments, the process can comprise a further step 4) working up the mixture. In some embodiments, the isocyanate functional compound can be a thioisocyanate of the formula R²NCS, wherein the definition of R² is the same as that given above.

[95] In still further embodiments, the process can comprise steps 1 ) and 3) above and step 2) of contacting the one or more structures according to A, B and/or C with an alcohol or thiol having a formula according to R²GH, in the presence of a carbodimidazole and a base, wherein R² and G are as defined above. Suitable bases can include, for example, tertiary amines, trialkyl amines, pyridine, 1 ,8-diazabicycloundec-7-ene, N,N- diisopropylethylamine, triethylamine, sodium carbonate or sodium hydrogen carbonate. The above process forms a synthetic mixture wherein the products formed comprise urethane or thiourethane linkages. Other methods for making such urethane and thiourethanes are known to one of ordinary skill and could be used. For example, the one or more compounds A, B and/or C comprise primary amines. Various methods are known for transforming a primary amine into an isocyanate or a

thioisocyanate group, for example, by the action of phosgene or

triphosgene. Once the one or more compounds A, B and/or C have been modified to comprise the isocyanates or thioisocyanates, contacting these intermediates with an alcohol R²GH would form the desired synthetic mixture.

[96] The R² group of the R²C(G)Z acylating agent or the R²NCG isocyanate is the same as defined above. If R² is unsaturated, the group can be mono-unsaturated, while in other embodiments, it can be di- or tri- unsaturated.

[97] Step 4) of the process, 'working up' means that the formed mixture is isolated by one of the known methods. In some embodiments, the formed synthetic mixture can be added to water and the desired products extracted into a suitable organic liquid. The organic liquid can then be dried and evaporated to give the desired synthetic mixture. In other embodiments, the liquid carrier of the formed synthetic mixture can be evaporated under reduced pressure and the resulting solid can be washed with water and filtered to give the desired synthetic mixture. Other methods of working up reaction mixtures are known in the art and can be used. A suitable liquid carrier can include, for example, dimethyl formamide, dimethyl sulfoxide, water, or other known organic solvents.

[98] In some embodiments, R² can be defined as the group -R⁴-R⁵-R⁶, wherein each each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C₁₂ alkylene, C₂ to C₁₂ alkenylene or C₂ to C₁₂ alkynylene; each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-; each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C₁₂ alkyl, C₂ to C₁₂ alkenyl, or C₂ to C₁₂ alkynyl; each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i, -NO₂, -N₃, -OR¹, SR¹, N(R¹)₂, and Ci to C₆ alkyl; and q is 1 to 6. [99] Examples of arylene and heteroarylene groups suitable for R⁴ include a variety of structures as shown below. Note that for these structures, the points of attachment to A, to R⁵ and to the optional R⁷ can be at any open position on the ring(s).

Wherein each R⁷, if present, is independently halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i, -NO₂, -N₃, -OR¹, SR¹, N(R¹)₂, and Ci to C6 alkyl; and q is 1 to 6.

[100] R⁵ is a linking group which links together R⁴ and R⁶. Suitable examples for R⁵ are -O-, -S-, -N(R¹)- or -NHC(O)-. In some embodiments, R⁵ is -O-. [101] Examples of aryl and heteroaryl groups suitable for R⁶ include a variety of aryl and heteroaryl structures as shown below. Note that for these structures, the points of attachment to R⁵ and to the optional R⁷ can be at any open position on the ring(s).

[102] Suitable examples of R²C(O)Z wherein R² is equal to R⁴R⁵R⁶ and Z is -OH can include, for example,



In each of the cases above, the O-linked or N-linked alkenyl chain can be at the 0-, m- or p- position of the aryl ring or positions 2-, 4-, 5- or 6- of the pyridine ring. Additionally, with the double bond is shown as a trans- isomer, the cis- isomer could also be used. Synthesis of the O-linked benzoic acid examples can be found in WO2005063784 A1 . Other examples and synthesis methods would be available to one of ordinary skill in the art.

[103] The synthetic mixtures described above, comprising two or more of the synthetic compounds (1 -1 ) through (4-4) find particular use in agricultural compositions and are useful as seed treatment formulation, as a seed coating composition, as a foliar formulation, as a sprayable foliar formulation or as a formulation suitable for treating the growing medium.

In some embodiments, the agricultural composition comprises an aqueous solution of the disclosed synthetic mixture. Seed treatment formulations typically contain in the range from about 10^"3 M to 10^"12 M of the two or more synthetic compounds. The concentration is based on the total concentration of all of the two or more synthetic compounds in the agricultural composition. In another embodiment, the agricultural formulations contain from about 10^"5 M to 10^"10 M of the two or more synthetic compounds. The locus of the propagating materials can be treated with the agricultural composition by many different methods. All that is needed is for a biologically effective amount of the synthetic mixture to be applied on or sufficiently close to the propagating material so that it can be absorbed by the propagating material. The agricultural

composition can be applied by such methods as drenching the growing medium including a propagating material with a solution or dispersion of the agricultural composition, mixing the agricultural composition with growing medium and planting a propagating material in the treated growing medium (e.g., nursery box treatments), or various methods of propagating material treatment whereby the agricultural composition is applied to a propagating material before it is planted in a growing medium. In some embodiments, the agricultural composition can provide an increased rate of germination, an increased rate of seedling emergence, an increased rate of radicle growth, an increased rate of early growth, increased pest control, increased disease control, increased plant height, increased vigor, increased resistance to abiotic environmental stress, and increased biomass and/or yield. In other embodiments, the agricultural composition can provide increased yield.

[104] In one embodiment, the agricultural composition is a formulation that comprises an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent, a surfactant and one or more other additives. A wide variety of formulations are suitable for the agricultural compositions; the most suitable types of formulations depend upon the method of application being used. Suitable formulations can include agricultural formulations. The agricultural formulations may include, for example, liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or

suspoemulsions) any of which optionally can be thickened into gels. Other useful formulations can include, for example, solids such as dusts, powders, granules, pellets, tablets and/or films, which can be

water-dispersible ("wettable") or water-soluble. The two or more synthetic compounds which form a part of the agricultural composition can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the two or more synthetic compounds. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength formulations are primarily used as intermediates for further formulation. [105] The formulations will typically contain effective amounts of the synthetic mixture, diluent and surfactant within the following approximate ranges that add up to 100 percent by weight.

Weight Percent

2 or more

synthetic Diluent Surfactant compounds

Water-Dispersible and 5-90 0-94 1 -15 Water-soluble Granules,

Tablets and Powders.

Suspensions, Emulsions, 5-50 40-95 0-15 Solutions (including

Emulsifiable Concentrates)

Dusts 1 -25 70-99 0-5

Granules and Pellets 0.01 -99 5-99.99 0-15

High Strength Formulations 90-99 0-10 0-2

[106] Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Emulsifiers and Detergents and McCutcheon's Functional Materials (North America and International Editions, 2001 ), The Manufactuing Confection Publ. Co., Glen Rock, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce, for example, foam, caking, corrosion, microbiological growth; or thickeners to increase viscosity.

[107] Surfactants include, for example, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated sorbitan fatty acid esters, ethoxylated amines, ethoxylated fatty acids, esters and oils, dialkyl sulfosuccinates, alkyl sulfates, alkylaryl sulfonates, organosilicones, Λ/,/V-dialkyltaurates, glycol esters, phosphate esters, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and block polymers including polyoxyethylene/polyoxypropylene block copolymers.

[108] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents can include, for example, water, or an organic diluent, for example, Λ/,/V-dimethylformamide, dimethyl sulfoxide, ethyl acetate, diethyl ether, formamide, 2-pyrrolidone, N-methylpyrrolidone, /V-alkylpyrrolidone, ethylene glycol, polypropylene glycol, 1 ,3-propane diol, 1 ,3-propane diol polyethers, alkyl and dialkyl ethers of 1 ,3-propane diol, alkyl and dialkyl ethers of 1 ,3-propane diol polyethers, diethylene glycol, diethylene glycol ethers, dipropylene glycol ethers, diglyme, hexamethylene glycol, pentamethylene glycol,

polyethylene glycol, poly hydroxy I ated alkanes, propylene glycol ethers, tetramethylene glycol, tetramethylene glycol ethers, triethylene glycol, triethylene glycol ethers, tripropylene glycol, tripropylene glycol ethers, 1 ,3- butylene glycol, 1 ,3-butylene glycol ethers, butylene carbonate, glycerol, thiodiglycol, propylene carbonate, dibasic esters, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as, for example, acetone, gamma-butyrolactone, methyl ethyl ketone, cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as, for example, C1 to C12 aliphatic alcohols, diacetone alcohol, ethanol, furfuryl alcohol,

tetrahydrofurfuryl alcohol polyethylene glycol ether, isopropanol, propanol, methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol, phosphoric acid esters, sulfolane, tetrahydrofuran or a combination thereof.

[109] In some embodiments, the agricultural composition can comprise in the range of 80 to 100 percent by weight of water, based on the total weight of the liquid diluent. In other embodiments, the liquid diluent can comprise in the range of from 90 to 100 percent water, and, in still further embodiments, in the range of from 95 to 100 percent water, wherein the percentages by weight are based on the total amount of the liquid diluent. The remaining amount of liquid diluent can be one or more of the organic diluents listed above.

[110] Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the synthetic mixture upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp. 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp. 8-57 and following, and PCT Publication WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as disclosed in U.S. 4,144,050, U.S. 3,920,442 and

DE 3,246,493. Tablets can be prepared as disclosed in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as disclosed in GB 2,095,558 and U.S. 3,299,566.

[111] Further information regarding the art of formulation can be found in the following publications; T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and

Bioscience, The Food-Environment Challenge, T. Brooks and

T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361 , Col. 6, line 16 through Col. 7, line 19 and Examples 10-41 ; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41 , 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891 ,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1 -4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , pp. 81 -96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989. [112] In order to inhibit or prevent microbial growth, one or more biocides can be added. Suitable biocides can include, for example, 5-chloro-2- methyl-3(2H)-isothiazolone , o-phenylphenol, sodium-o-phenylphenate, cis-1 -(chloroallyl)-3,5,7-triaza-1 -azoniaadamantane chloride, 7-ethyl bicyclooxazolidine, 2,2-dibromo-3-nitrilopropionamide, bronopol, glutaraldehyde, copper hydroxide, cresol, dichlorophen, dipyrithione, fenaminosulf, formaldehyde, hydrargaphen, 8-hydroxyquinoline sulfate, kasugamycin, nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, thimerosal, polyquaternary ammonium chloride, alkylbenzyl dimethyl ammonium chloride, 2-methyl-4- isothiazolone, 2-ethyl-4-isothiazolin-3-one, 2-propyl-4-isothiazolin-3-one, 2-butyl-4-isothiazolin-3-one, 2-amyl-4-isothiazolin-3-one, 5-chloro-2- methyl-4-isothiazolin-3-one, 5-bromo-2-methyl-4-isothiazolin-3-one, 5- iodo-2-methyl-4-isothiazolin-3-one, 5-chloro-2-butyl-4-isothiazolin-3-one, 5-bromo-2-ethyl-4-isothiazolin-3-one, 5-iodo-2-amyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothazolin-3-one, 1 ,2-benzisothiazolin-3-one or a combination thereof.

[113] The agricultural compositions used for treating propagating materials, or plants grown therefrom, can also comprise an effective amount of one or more other biologically active compounds or agents. Suitable additional compounds or agents include, but are not limited to, insecticides, fungicides, nematocides, bactericides, acaricides,

entomopathogenic bacteria, viruses, fungi, microorganisms; growth regulators such as rooting stimulants, chemosterilants, repellents, attractants, pheromones, feeding stimulants and other signal compounds including apocarotenoids, flavonoids, jasmonates and strigolactones (Akiyama, et al., in Nature, 435:824-827 (2005); Harrison, in Ann. Rev. Microbiol., 59:19-42 (2005); Besserer, et al., in PLoS Biol., 4(7):e226 (2006); WO2009049747). Polymeric polyhydroxy acids, such as,

ARCUS™ ST, available from FBSciences, Coll ierville, Tennessee can also be added. Combinations if the biologically active compounds can also be used. Biologically active agents according to this disclosure can also comprise microorganisms that stimulate plant growth. Such microorganisms include, but are not limited to, biologically active species within the bacterial genera Azorhizobium, Bacillus, Bradyrhizobium, Mesorhizobium, Paenibacillus and Rhizobium (Khan, et al., in Bioresource Technology, 99(8): 3016-3023 (2008); Plant Growth and Health Promoting Bacteria (Microbiology Monographs), D. K. Maheshwari, Ed., Springer- Verlag, Berlin, 2010. Such microorganisms also include, but are not limited to, plant growth promoting species within the fungal genera

Cladosporum, Corvularia, Fusarium, Gliocladium, Metarhizium, Penicilliunn and Trichoderma (Kim, et al. in BMC Microbiology, 8:231 (2008); Khan, et al., in World Journal of Microbiology and Biotechnology, 28(4): 1483-1494 (2012), Biotechnology of Microbes and Sustainable Utilization,

R. C. Rajak, Ed., Scientific Publishers, Jodhpur, India, 2002, pp. 1 16-120. These agents can be formulated into the agricultural composition giving an even broader spectrum of agricultural utility than can be achieved with the synthetic mixture alone. Combinations of these biologically active compounds or agents can also be used.

[114] Examples of such biologically active compounds or agents with which can be mixed or formulated as a part of the agricultural composition include, for example, insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin,

azinphos-methyl, bifenthrin, binfenazate, buprofezin, carbofuran, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos- methyl, chromafenozide, clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothicarb, fenoxycarb, fenpropathrin, fenproximate, fenvalerate, fipronil, flonicamid, flucythrinate, flupyradifurone, tau-fluvalinate, flufenerim (UR-50701 ), flufenoxuron, fonophos, halofenozide, hexaflumuron, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaldehyde,

methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, methoxyfenozide, nithiazin, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, pymetrozine, pyridalyl, pyriproxyfen, rotenone, spinosad, spiromesifin (BSN 2060), sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos,

tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap- sodium, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar, azoxystrobin, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, (S)-3,5-dichloro-/V-(3- chloro-1 -ethyl-1 -methyl-2-oxopropyl)-4-methylbenzamide (RH 7281 ), diclocymet (S-2900), diclomezine, dicloran, difenoconazole, (S)-3,5- dihydro-5-methyl-2-(methylthio)-5-phenyl-3-(phenylamino)-4/-/-imidazol-4- one (RP 407213), dimethomorph, dimoxystrobin, diniconazole,

diniconazole-M, dodine, edifenphos, epoxiconazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid (SZX0722), fenpidonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, fluazinam, fludioxonil, flumetover (RPA 403397), flumorf/flumorlin (SYP-L190), fluoxastrobin (HEC 5725), fluquinconazole, flusilazole, flutolanil, fluopyram, flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658), hexaconazole, ipconazole, iprobenfos, iprodione,

isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole,

metominostrobin/fenominostrobin (SSF-126), metrafenone (AC 375839), myclobutanil, neo-asozin (ferric methanearsonate), nicobifen (BAS 510), orysastrobin, oxadixyl, oxathiapiprolin, penconazole, pencycuron, penflufen, penthiopyrad, picoxystrobin, probenazole, prochloraz, propamocarb, propiconazole, proquinazid, prothioconazole (JAU 6476), pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen, sedaxane, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tiadinil, triadimefon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin and vinclozolin;

nematocides such as aldicarb, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents including Bacillus thuringiensis (including ssp. aizawai and kurstaki), Bacillus thuringiensis delta-endotoxin, Bacillus firmus 1-1582, Bacillus simplex, Pasteuria nishizawae, baculoviruses, and entomopathogenic bacteria, viruses, as well as naturally occurring and genetically modified viral insecticides including members of the family Baculoviridae and fungi, including entomophagous fungi. A general reference for these agricultural protectants is The Pesticide Manual, 12th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2000.

Combinations of any of the above mentioned can also be used.

[115] Two particular Bacillus strains that can be used are Bacillus amyloliquifaciens 22CP1 (ATCC PTA-6508) and Bacillus amyloliquifaciens 15AP4 (ATCC PTA-6507). On January 12, 2005, Bacillus

amyloliquifaciens 22CP1 was deposited at the American Type Culture Collection (ATCC), 10801 University Blvd., Manassas, Virginia 201 10- 2209 and given accession number PTA-6508. The deposits were made under the provisions of the Budapest Treaty on the International

Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure. Also on January 12, 2005, Bacillus amyloliquifaciens 15AP4 was deposited at the American Type Culture Collection (ATCC), 10801 University Blvd., Manassas, Virginia 201 10-2209 and given accession numbers PTA-6507. The deposit was made under the provisions of the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure.

[116] In some embodiments, the agricultural composition can comprise the synthetic mixture and Bacillus amyloliquifaciens 22CP1 . In other embodiments, the agricultural composition can comprise the synthetic mixture and Bacillus amyloliquifaciens 15AP4.

[117] The anthranilamide insecticides, which include chlorantraniliprole and cyantraniliprole, comprises a large class of compounds having insecticidal activity. The agricultural composition can further comprise and one of the compounds of Formula 1 including N-oxides or salts therefrom;

wherein

X is N, CF, CCI, CBr or CI;

R⁷ is CH₃, CI, Br or F;

R⁸ is H, F, CI, Br or -CN;

R⁹ is F, CI, Br, C1 to C4 haloalkyl, C1 to C4 haloalkoxy or Q;

R¹⁰ is NR¹³R¹⁴, N=S(CH₃)₂, N=S(CH₂CH₃)₂, N=S(CH(CH₃)₂)2;

R¹¹ is H, F, CI or Br;

R¹² is H, F, CI or Br;

each R¹³ and R¹⁴ is independently H, C1 to C6 alkyl, C3 to C6 cycloalkyl, cyclopropyl methyl or 1 -cyclopropylethyl; and

Q is a -CH₂-tetrazole radical. Suitable embodiments for Q can include any structure having a formula according to Q-1 to Q-1 1 ;

[118] In other embodiments, the agricultural composition can further comprise any of the known anthranilic diamide insecticides, for example, those described in US 6,747,047, US 8,324,390, US 2010/0048640,

WO 2007/006670, WO 2013/024009, WO 2013/024010,

WO 2013/024004, WO 2013/024170 or WO 2013/024003. Specific embodiments from US 8,324,390 can include any of those compounds disclosed as examples 1 through 544. Specific embodiments from

US 2010/0048640 can include any of those compounds disclosed in

Tables 1 through 68 or compounds represented by Chemical Formula 44 through 1 18. Each of the references to the above patents and

applications are hereby incorporated by reference. [119] The agricultural compositions comprising the salt complex of Structure A can further comprise one or more signal molecules. In plants of the Leguminoseae family, the symbiotic interaction between the plants and nitrogen-fixing bacteria of the Rhizobiaceae family ("rhizobia") enhances plant growth and crop yield. The symbiotic interaction is initiated when a plant releases flavonoid compounds that stimulate rhizobia! bacteria in the soil to produce lipochitooligosaccharide signal molecule (LCOs).

[120] LCOs are signaling compounds that induce the early stages of nodulation in plant roots, which lead to the formation of root nodules containing the nitrogen-fixing rhizobial bacteria. Application of a LCO to seeds of legumes and non-legumes can help to stimulate germination, seedling emergence, plant growth and yield in crop and horticultural plant species. LCOs have also been shown to enhance root development. Foliar application of LCOs has also been demonstrated to increase photosynthesis, and fruiting and flowering in crop and horticultural plant species.

[121] LCOs consist of an oligomeric backbone of β-1 ,4-linked N-acetyl-D- glucosamine ("GlcNAc") residues with an N-linked fatty acyl chain at the nonreducing end. LCOs differ in the number of GlcNAc residues in the backbone, in the length and degree of saturation of the fatty acyl chain, and in the substitutions of reducing and nonreducing sugar residues. LCO structure is characteristic for each rhizobial species, and each strain may produce multiple LCO's with different structures. LCO's are the primary determinants of host specificity in legume symbiosis.

[122] In one embodiment, the bacterial strains disclosed herein can be used with one or more LCOs. In one embodiment, the disclosure relates to the agricultural composition and further comprising a bacterial strain disclosed herein and one or more LCOs. In still yet another embodiment, the agricultural composition can further comprise one or more LOCs. Suitable LCOs are known in the art and can be found in, for example, US 5,175,149 to The University of Tennessee Research Corporation; US 5,549,718 to Centre National de la Recherche Scientifique; and WO2012/20105 to Bayer Crop Science.

[123] Suitable plant growth regulators for mixing or formulating the agricultural compositions for treating stem cuttings are 1 H-indole-3-acetic acid, 1 H-indole-3-butanoic acid and 1 -naphthaleneacetic acid and their agriculturally suitable salt, ester and amide derivatives, such as

1 -napthaleneacetamide. In some embodiments, the fungicides can include, for example, thiram, maneb, mancozeb and captan.

[124] In some embodiments, microorganisms can be added to the agricultural composition. Suitable examples of microorganisms, can include, for example, a phosphate solubilizing microorganism. As used herein, "phosphate solubilizing microorganism" is a microorganism that is able to increase the amount of phosphorous available for a plant.

Phosphate solubilizing microorganisms include fungal and bacterial strains. In one embodiment, the phosphate solubilizing microorganism is a spore forming microorganism.

[125] In some embodiments, the phosphate solubilizing microorganisms can include, for example, species from a genus selected from the group consisting of Acinetobacter, Arthrobacter, Arthrobotrys, Aspergillus, Azospirillum, Bacillus, Burkholderia, Candida Chryseomonas,

Enterobacter, Eupenicillium, Exiguobacterium, Klebsiella, Kluyvera, Microbacterium, Mucor, Paecilomyces, Paenibacillus, Penicillium,

Pseudomonas, Serratia, Stenotrophomonas, Streptomyces,

Streptosporangium, Swaminathania, Thiobacillus, Torulospora, Vibrio, Xanthobacter, and Xanthomonas.

[126] In further embodiments, the phosphate solubilizing microorganisms can include, for example, Acinetobacter calcoaceticus, Acinetobacter sp, Arthrobacter sp., Arthrobotrys oligospora, Aspergillus niger, Aspergillus sp., Azospirillum halopraeferans, Bacillus amyloliquefaciens, Bacillus atrophaeus, Bacillus circulans,Bacillus licheniformis, Bacillus subtilis, Burkholderia cepacia, Burkholderia vietnamiensis, Candida krissii,

Chryseomonas luteola, Enterobacter aerogenes, Enterobacter asburiae, Enterobacter sp., Enterobacter taylorae, Eupenicillium parvum, Exiguobacterium sp., Klebsiella sp., Kluyvera cryocrescens,

Microbacterium sp., Mucor ramosissimus, Paecilomyces hepialid,

Paecilomyces marquandii, Paenibacillus macerans, Paenibacillus mucilaginosus, Pantoea aglomerans, Penicillium expansum,

Pseudomonas corrugate, Pseudomonas fluorescens, Pseudomonas lutea, Pseudomonas poae, Pseudomonas putida, Pseudomonas stutzeri, Pseudomonas trivialis, Serratia marcescens, Stenotrophomonas maltophilia, Streptomyces sp., Streptosporangium sp., Swaminathania salitolerans, Thiobacillus ferrooxidans, Torulospora globosa, Vibrio proteolytics, Xanthobacter agilis, and Xanthomonas campestris.

[127] In a particular embodiment, the phosphate solubilizing

microorganism is a strain of the fungus Penicillium. Strains of the fungus Penicillium that may be useful in the practice of the present disclosure include P. bilaiae (formerly known as P. bilaii), P. albidum, P.

aurantiogriseum, P. chrysogenum, P. citreonigrum, P. citrinum, P.

digitatum, P. frequentas, P. fuscum, P. gaestrivorus, P. glabrum, P.

griseofulvum, P. implicatum, P. janthinellum, P. Iilacinum, P. minioluteum, P. montanense, P. nigricans, P. oxalicum, P. pinetorum, P. pinophilum, P. purpurogenum, P. radicans, P. radicum, P. raistrickii, P. rugulosum, P. simplicissimum, P. solitum, P. variabile, P. velutinum, P. viridicatum, P. glaucum, P. fussiporus, and P. expansum.

[128] In another particular embodiment, the Penicillium species is P. bilaiae. In still another particular embodiment the P. bilaiae strains are selected from the group consisting of American Type Culture Collection (ATCC) ATCC 20851 , Northern Regional Research Laboratory (NRRL) NRRL 50169, ATCC 22348, ATCC 18309, NRRL 50162 (Wakelin, et al., 2004. Biol Fertil Soils 40:36-43). In another particular embodiment the Penicillium species is P. gaestrivorus, e.g., NRRL 50170 (see, Wakelin, supra.).

[129] In some embodiments, more than one phosphate solubilizing microorganism is used, for example, at least two, at least three, at least four, at least five, at least 6, including, for example, any combination of the Acinetobacter, Arthrobacter, Arthrobotrys, Aspergillus, Azospirillum, Bacillus, Burkholderia, Candida Chryseomonas, Enterobacter,

Eupenicillium, Exiguobacterium, Klebsiella, Kluyvera, Microbacterium, Mucor, Paecilomyces, Paenibacillus, Penicillium, Pseudomonas, Serratia, Stenotrophomonas, Streptomyces, Streptosporangium, Swaminathania, Thiobacillus, Torulospora, Vibrio, Xanthobacter, and Xanthomonas, including one species selected from the following group: Acinetobacter calcoaceticus, Acinetobacter sp, Arthrobacter sp., Arthrobotrys oligospora, Aspergillus niger, Aspergillus sp., Azospirillum halopraeferans, Bacillus amyloliquefaciens, Bacillus atrophaeus, Bacillus circulans, Bacillus licheniformis, Bacillus subtilis, Burkholderia cepacia, Burkholderia vietnamiensis, Candida krissii, Chryseomonas luteola, Enterobacter aerogenes, Enterobacter asburiae, Enterobacter sp., Enterobacter taylorae, Eupenicillium parvum, Exiguobacterium sp., Klebsiella sp., Kluyvera cryocrescens, Microbacterium sp., Mucor ramosissimus,

Paecilomyces hepialid, Paecilomyces marquandii, Paenibacillus macerans, Paenibacillus mucilaginosus, Pantoea aglomerans, Penicillium expansum, Pseudomonas corrugate, Pseudomonas fluorescens,

Pseudomonas lutea, Pseudomonas poae, Pseudomonas putida,

Pseudomonas stutzeri, Pseudomonas trivialis, Serratia marcescens, Stenotrophomonas maltophilia, Streptomyces sp., Streptosporangium sp., Swaminathania salitolerans, Thiobacillus ferrooxidans, Torulospora globosa, Vibrio proteolytics, Xanthobacter agilis, and Xanthomonas campestris.

[130] In some embodiments, two different strains of the same species may also be combined, for example, at least two different strains of Penicillium are used. The use of a combination of at least two different Penicillium strains has the following advantages. When applied to soil already containing insoluble (or sparingly soluble) phosphates, the use of the combined fungal strains will result in an increase in the amount of phosphorus available for plant uptake compared to the use of only one Penicillium strain. This in turn may result in an increase in phosphate uptake and/or an increase in yield of plants grown in the soil compared to use of individual strains alone. The combination of strains also enables insoluble rock phosphates to be used as an effective fertilizer for soils which have inadequate amounts of available phosphorus. Thus, in some embodiments, one strain of P. bilaiae and one strain of P. gaestrivorus are used. In other embodiments, the two strains are NRRL 50169 and NRRL 50162. In further embodiments, the at least two strains are NRRL 50169 and NRRL 50170. In yet further embodiments, the at least two strains are NRRL 50162 and NRRL 50170.

[131] The phosphate solubilizing microorganisms may be prepared using any suitable method known to the person skilled in the art, such as, solid state or liquid fermentation using a suitable carbon source. These culture methods may be used in the preparation of an inoculum of Penicillium spp. for treating seeds and/or application to an agrononnically acceptable carrier to be applied to soil. The term "inoculum" as used in this specification is intended to mean any form of phosphate solubilizing microorganism, fungus cells, mycelium or spores, bacterial cells or bacterial spores, which is capable of propagating on or in the soil, including on or in the vicinity of plant roots when the conditions of temperature, moisture, etc., are favorable for fungal growth. The phosphate solubilizing microorganism is preferably prepared in the form of a stable spore.

[132] Solid state production of Penicillium spores may be achieved by inoculating a solid medium such as a peat or vermiculite-based substrate, seeds or grains including, but not limited to, corn, soy, potato, oats, wheat, barley, or rice. The sterilized medium (achieved through autoclaving or irradiation) is inoculated with a spore suspension comprising in the range of from 1 x10²-1 x10⁷ colony forming units per milliliter (cfu/ml) of the appropriate Penicillium spp. and the moisture adjusted to 20 to 50%, depending on the substrate. The inoculated medium is incubated for 2 to 8 weeks at room temperature. The spores may also be produced by liquid fermentation (Cunningham et al., 1990. Can J Bot. 68:2270-2274). Liquid production may be achieved by cultivating the fungus in any suitable media, such as potato dextrose broth or sucrose yeast extract media, under appropriate pH and temperature conditions that may be determined in accordance with standard procedures in the art. [133] The resulting material may be used directly, or the spores may be harvested, concentrated by centrifugation, formulated, and then dried using air drying, freeze drying, or fluid bed drying techniques (Friesen, et ai, 2005, Appl. Microbiol. Biotechnol. 68:397-404) to produce a wettable powder. The wettable powder is then suspended in water, applied to the surface of seeds, and allowed to dry prior to planting. The wettable powder may be used in conjunction with other seed treatments, such as, but not limited to, chemical seed treatments, carriers (for example, talc, clay, kaolin, silica gel, kaolinite) or polymers (for example, methylcellulose, polyvinylpyrrolidone). Alternatively, a spore suspension of the appropriate Penicillium spp. may be applied to a suitable soil-compatible carrier (for example, peat-based powder or granule) to appropriate final moisture content. The material may be incubated at room temperature, typically for about 1 day to about 8 weeks, prior to use.

[134] The amount of the at least one phosphate solubilizing

microorganism varies depending on the type of seed or soil, the type of plant material, the amounts of the source of phosphorus and/or

micronutrients present in the soil or added thereto, etc. A suitable amount can be found by simple trial and error experiments for each particular case. Normally, for Penicillium, for example, the application amount falls into the range of from 0.001 to 1 .0 Kg fungal spores and mycelium (fresh weight) per hectare, or 10²-10⁶ colony forming units (cfu) per seed (when coated seeds are used), or on a granular carrier applying between 1 x10⁶ and 1 x10^{1 1} colony forming units per hectare. The fungal cells in the form of e.g., spores and the carrier can be added to a seed row of the soil at the root level or can be used to coat seeds prior to planting.

[135] Diazotrophs are bacteria and archaea that fix atmospheric nitrogen gas into a more usable form such as ammonia. Examples of diazotrophs include bacteria from the genera Rhizobium spp. (e.g., R. cellulosilyticum, R. daejeonense, R. etli, R. galegae, R. gallicum, R. giardinii, R.

hainanense, R. huautlense, R. indigoferae, R. leguminosarum, R.

loessense, R. lupini, R. lusitanum, R. meliloti, R. mongolense, R.

miluonense, R. sullae, R. tropici, R. undicola, and/or R. yanglingense), Bradyrhizobium spp. (e.g., B. bete, B. canariense, B. elkanii, B.

iriomotense, B. japonicum, B. jicamae, B. liaoningense, B. pachyrhizi, and/or B. yuanmingense), Azorhizobium spp. (e.g., A. caulinodans and/or A. doebereinerae), Sinorhizobium spp. (e.g., S. abri, S. adhaerens, S. americanum, S. aborts, S. fredii, S. indiaense, S. kostiense, S.

kummerowiae, S. medicae, S. meliloti, S. mexicanus, S. morelense, S. saheli, S. terangae, and/or S. xinjiangense), Mesorhizobium spp., (M. albiziae, M. amorphae, M. chacoense, M. ciceri, M. huakuii, M. loti, M. mediterraneum, M. pluifarium, M. septentrionale, M. temperatum, and/or M. tianshanense), and combinations thereof. In a particular embodiment, the diazotroph is selected from the group consisting of B. japonicum, R leguminosarum, R meliloti, S. meliloti, and combinations thereof. In another embodiment, the diazotroph is B. japonicum. In another embodiment, the diazotroph is R leguminosarum. In another embodiment, the diazotroph is R meliloti. In another embodiment, the diazotroph is S. meliloti.

[136] Mycorrhizal fungi form symbiotic associations with the roots of a vascular plant, and provide, e.g., absorptive capacity for water and mineral nutrients due to the comparatively large surface area of mycelium.

Mycorrhizal fungi include endomycorrhizal fungi (also called vesicular arbuscular mycorrhizae, VAMs, arbuscular mycorrhizae, or AMs), an ectomycorrhizal fungi, or a combination thereof. In one embodiment, the mycorrhizal fungi is an endomycorrhizae of the phylum Glomeromycota and genera Glomus and Gigaspora. In still a further embodiment, the endomycorrhizae is a strain of Glomus aggregatum, Glomus brasilianum, Glomus clarum, Glomus deserticola, Glomus etunicatum, Glomus fasciculatum, Glomus intraradices, Glomus monosporum, or Glomus mosseae, Gigaspora margarita, or a combination thereof.

[137] Examples of mycorrhizal fungi include ectomycorrhizae of the phylum Basidiomycota, Ascomycota, and Zygomycota. Other examples include a strain of Laccaria bicolor, Laccaria laccata, Pisolithus tinctorius, Rhizopogon amylopogon, Rhizopogon fulvigleba, Rhizopogon luteolus, Rhizopogon villosuli, Scleroderma cepa, Scleroderma citrinum, or a combination thereof.

[138] The mycorrhizal fungi include ecroid mycorrhizae, arbutoid mycorrhizae, or monotropoid mycorrhizae. Arbuscular and

ectomycorrhizae form ericoid mycorrhiza with many plants belonging to the order Ericales, while some Ericales form arbutoid and monotropoid mycorrhizae. In one embodiment, the mycorrhiza may be an ericoid mycorrhiza, for example, of the phylum Ascomycota, such as

Hymenoscyphous ericae or Oidiodendron sp. In another embodiment, the mycorrhiza also may be an arbutoid mycorrhiza, for example, of the phylum Basidiomycota. In yet another embodiment, the mycorrhiza may be a monotripoid mycorrhiza, for example, of the phylum Basidiomycota. In still yet another embodiment, the mycorrhiza may be an orchid mycorrhiza, for example, of the genus Rhizoctonia.

[139] In some embodiments, the agricultural composition can comprise the synthetic mixture and combination of any of the above listed components. For example, the agricultural composition can comprise a combination of two different insecticides, a fungicide and any one or more of the above listed bacterial or fungal strains. In other embodiments, the agricultural composition can comprise the synthetic mixture and chlorantraniliprole , cyantraniliprole or a combination of chlorantraniliprole and cyantraniliprole and one or more of the ingredients in Table 1 of rows 1 , 2 or 3.

TABLE 1

[140] The agricultural composition can be applied by such methods as drenching the growing medium including a propagating material with a solution or dispersion of the agricultural composition, mixing the agricultural composition with growing medium and planting a propagating material in the treated growing medium (e.g., nursery box treatments), or various methods of propagating material treatment whereby the

agricultural composition is applied to a propagating material before it is planted in a growing medium.

[141] For agricultural compositions that are applied as growing-medium drenches, formulations can provide the disclosed synthetic mixture, generally after dilution with water, in solution or as particles small enough to remain dispersed in the liquid. Water-dispersible or soluble powders, granules, tablets, emulsifiable concentrates, aqueous suspension concentrates and the like are formulations suitable for aqueous drenches of growing media. Drenches are most satisfactory for treating growing media that have relatively high porosity, such as light soils or artificial growing medium comprising porous materials such as peat moss, perlite, vermiculite and the like. The drench liquid comprising the disclosed synthetic mixture can also be added to a liquid growing medium (i.e.

hydroponics), which causes the synthetic compound to become a component of the liquid growing medium. One skilled the art will appreciate that the amount of the disclosed two or more synthetic compounds needed in the drench liquid for efficacy (i.e. biologically effective amount) will vary with several factors including, but not limited to, plant species, propagating material type and environmental conditions. The concentration of the two or more synthetic compounds in the drench liquid is generally between about 10^"3 M to 10^{"1 1} M of the composition, more typically between about 10^"5 M to 10^"10 M. One skilled in the art can easily determine the biologically effective concentration necessary for the desired level of efficacy.

[142] For treating a growing medium, the agricultural composition can also be applied by mixing it as a dry powder or granule formulation with the growing medium. Because this method of application does not require first dispersing or dissolving in water, the dry powder or granule

formulations need not be highly dispersible or soluble. While in a nursery box the entire body of growing medium may be treated, in an agricultural field only the soil in the vicinity of the propagating material is typically treated for environmental and cost reasons. To minimize application effort and expense, a formulation containing the disclosed synthetic mixture is most efficiently applied concurrently with propagating material planting (e.g., seeding). For in-furrow application, the formulation (most

conveniently a granule formulation) is applied directly behind the planter shoe. For T-band application, the formulation is applied in a band over the row behind the planter shoe and behind or usually in front of the press wheel. One skilled the art will appreciate that the amount of synthetic mixture needed for efficacy (i.e. biologically effective amount) will vary with several factors including, but not limited to, plant species, propagating material type and environmental conditions. The concentration of the two or more synthetic compounds in the growing medium locus is generally between about 10^"3 M to 10^"11 M of the agricultural composition, more typically between about 10^"5 M to 10^"10 M. One skilled in the art can easily determine the biologically effective amount necessary for the desired level of efficacy.

[143] In some embodiments, the disclosure also relates to a method of treating a propagule comprising the steps; a) providing the agricultural composition comprising the synthetic mixture; and b) contacting the propagule with the agricultural composition. A propagating material can be directly treated by soaking it in a solution or dispersion of the

agricultural composition. Although this application method is useful for propagating materials of all types, treatment of large seeds (e.g., having a mean diameter of at least 3 mm) is more effective than treatment of small seeds for providing efficacy. Treatment of propagating materials such as tubers, bulbs, corms, rhizomes and stem and leaf cuttings also can provide effective treatment of the developing plant in addition to the propagating material. The formulations useful for growing-medium drenches are generally also useful for soaking treatments. The soaking medium comprises a nonphytotoxic liquid, generally water-based although it may contain nonphytotoxic amounts of other solvents such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, propylene carbonate, benzyl alcohol, dibasic esters, acetone, methyl acetate, ethyl acetate, cydohexanone, dimethylsulfoxide and /V-methylpyrrolidone, which may be useful for enhancing solubility of synthetic mixture and penetration into the propagating material. A surfactant can facilitate wetting of the propagating material and penetration of the synthetic mixture. One skilled the art will appreciate that the amount of the two or more synthetic compounds needed in the soaking medium for efficacy (i.e. biologically effective amount) will vary with several factors including, but not limited to, plant species, propagating material type and environmental conditions. The concentration of the synthetic compounds in the soaking liquid is generally between about 10^"3 M to10^{"1 1} M of the agricultural composition, more typically between about 10^"5 M to 10^"10 M. One skilled in the art can easily determine the biologically effective concentration necessary for the desired level of efficacy. The soaking time can vary from one minute to one day or even longer. Indeed, the propagating material can remain in the treatment liquid while it is germinating or sprouting (e.g., sprouting of rice seeds prior to direct seeding). As shoot and root emerge through the testa (seed coat), the shoot and root directly contact the agricultural composition comprising the synthetic mixtures. For treatment of sprouting seeds of large-seeded crops such as rice, treatment times in the range of from about 8 to 48 hours, e.g., about 24 hours, is typical. Shorter times are most useful for treating small seeds.

[144] A propagating material can also be coated with the agricultural composition comprising the synthetic mixture. The coatings of the disclosure are capable of affecting a slow release of the synthetic mixture by diffusion into the propagating material and surrounding medium.

Coatings include dry dusts or powders adhering to the propagating material by action of a sticking agent such as methylcellulose or gum arabic. Coatings can also be prepared from suspension concentrates, water-dispersible powders or emulsions that are suspended in water, sprayed on the propagating material in a tumbling device and then dried. Agricultural compositions comprising the synthetic compounds that are dissolved in the solvent can be sprayed on the tumbling propagating material and the solvent then evaporated. Such agricultural compositions can include ingredients promoting adhesion of the coating to the propagating material. The agricultural compositions may also contain surfactants promoting wetting of the propagating material. Solvents used must not be phytotoxic to the propagating material; generally water is used, but other volatile solvents with low phytotoxicity such as methanol, ethanol, methyl acetate, ethyl acetate, acetone, etc. may be employed alone or in combination. Volatile solvents are those with a normal boiling point less than about 100°C. Drying must be conducted in a way not to injure the propagating material or induce premature germination or sprouting.

[145] The thickness of coatings can vary from adhering dusts to thin films to pellet layers about 0.5 to 5 mm thick. Propagating material coatings of this disclosure can comprise more than one adhering layer, only one of which is required to comprise the synthetic mixture. Generally pellets are most satisfactory for small seeds, because their ability to provide a biologically effective amount of the synthetic compounds are not limited by the surface area of the seed, and pelleting small seeds also facilitates seed transfer and planting operations. Because of their larger size and surface area, large seeds and bulbs, tubers, corms and rhizomes and their viable cuttings are generally not pelleted, but instead coated with powders or thin films.

[146] In some embodiments, propagating materials contacted with the agricultural composition can include seeds. Suitable seeds include seeds of wheat, durum wheat, barley, oat, rye, maize, sorghum, rice, wild rice, cotton, flax, sunflower, soybean, garden bean, lima bean, broad bean, garden pea, peanut, alfalfa, beet, garden lettuce, rapeseed, cole crop, turnip, leaf mustard, black mustard, tomato, potato, pepper, eggplant, tobacco, cucumber, muskmelon, watermelon, squash, carrot, zinnia, cosmos, chrysanthemum, sweet scabious, snapdragon, gerbera, babys- breath, statice, blazing star, lisianthus, yarrow, marigold, pansy, impatiens, petunia, geranium and coleus. Of note are seeds of cotton, maize, soybean and rice. In other embodiments, propagating materials contacted with the agricultural composition can also include rhizomes, tubers, bulbs or corms, or viable divisions thereof. Suitable rhizomes, tubers, bulbs and corms, or viable divisions thereof include those of potato, sweet potato, yam, garden onion, tulip, gladiolus, lily, narcissus, dahlia, iris, crocus, anemone, hyacinth, grape-hyacinth, freesia, ornamental onion, wood- sorrel, squill, cyclamen, glory-of-the-snow, striped squill, calla lily, gloxinia and tuberous begonia. Of note are rhizomes, tubers, bulbs and corms, or viable division thereof of potato, sweet potato, garden onion, tulip, daffodil, crocus and hyacinth. In still further embodiments, propagating materials contacted with the agricultural composition can also include stems and leaf cuttings.

[147] In some embodiments, a propagating material can be coated with an agricultural composition comprising the synthetic mixture and a film forming agent or adhesive agent. Agricultural compositions that contain a biologically effective amount of the synthetic mixture and film forming agent or adhesive agent, can optionally contain an effective amount of at least one of the previously mentioned biologically active compounds or agents. In some embodiments, a propagating material coating comprises the synthetic mixture, a film forming agent or adhesive agent. The coating may further comprise formulation aids such as a dispersant, a surfactant, a carrier and optionally an antifoam and dye. One skilled the art will appreciate that the two or more compounds needed for efficacy (i.e.

biologically effective amount) will vary with several factors including, but not limited to, plant species, propagating material type and environmental conditions. It is desired that the coating not inhibit germination or sprouting of the propagating material.

[148] The film forming agent or adhesive agent component of the propagating material coating can contains an adhesive polymer that may be natural or synthetic and is without phytotoxic effect on the propagating material to be coated. The film forming agent or adhesive agent can be selected from polyvinyl acetates, polyvinyl acetate copolymers, hydrolyzed polyvinyl acetates, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers, polyvinyl methyl ether, polyvinyl methyl ether-maleic anhydride copolymer, waxes, latex polymers, celluloses including ethylcelluloses and methylcelluloses, hydroxy- methylcelluloses, hydroxypropylcellulose, hydroxymethylpropylcelluloses, polyvinylpyrrolidones, alginates, dextrins, malto-dextrins, polysaccharides, fats, oils, proteins, karaya gum, jaguar gum, tragacanth gum,

polysaccharide gums, mucilage, gum arabics, shellacs, vinylidene chloride polymers and copolymers, soybean-based protein polymers and

copolymers, lignosulfonates, acrylic copolymers, starches,

polyvinylacrylates, zeins, gelatin, carboxymethylcellulose, chitosan, polyethylene oxide, acrylimide polymers and copolymers, polyhydroxyethyl acrylate, methylacrylimide monomers, alginate, ethylcellulose,

polychloroprene and syrups or mixtures thereof. Suitable film forming agents and adhesive agents include polymers and copolymers of vinyl acetate, polyvinylpyrrolidone-vinyl acetate copolymer and water-soluble waxes. In some embodiments, the film forming agents or adhesive agents can include polyvinylpyrrolidone-vinyl acetate copolymers and water- soluble waxes. The above-identified polymers include those known in the art and for example some are identified as AGRIMER^® VA 6

(Vinylpyrrolidone/vinyl acetate copolymers available from Ashland, Inc., Covington, KY) and LICOWAX^® KST (an ester of montanic acids with multifunctional alcohols available from Clariant International Ltd., Muttenz, Switzerland). The amount of film forming agent or adhesive agent in the formulation is generally in the range of about 0.001 to 100% of the weight of the propagating material. For large seeds the amount of film forming agent or adhesive agent is typically in the range of about 0.05 to 5% of the seed weight; for small seeds the amount is typically in the range of about 1 to 100%, but can be greater than 100% of seed weight in pelleting. For other propagating materials the amount of film forming agent or adhesive agent is typically in the range of 0.001 to 2% of the propagating material weight.

[149] Materials known as formulation aids may also be used in

propagating material treatment coatings of the disclosure and are well known to those skilled in the art. Formulation aids assist in the production or process of propagating material treatment and include, but are not limited, to dispersants, surfactants, carriers, antifoams and dyes. Useful dispersants can include highly water-soluble anionic surfactants like BORRESPERSE™ CA (a spray dried calcium lignosulphonate available from Borregaard Deutschland GmbH, Karlsruhe, Germany), MORWET^® D425 (naphthalene sulfonate available from AkzoNobel, Amsterdam, Netherlands) and the like. Useful surfactants can include highly water- soluble nonionic surfactants like PLURONIC^® F108 (a difunctional block copolymer surfactant available from BASF, Florham Park, NJ), BRIJ^® 78 (polyethylene glycol octadecyl ether available from Sigma-Aldrich, St. Louis. MO) and the like. Useful carriers can include liquids like water and oils which are water-soluble such as alcohols. Useful carriers can also include fillers like woodflours, clays, activated carbon, diatomaceous earth, fine-grain inorganic solids, calcium carbonate and the like. Clays and inorganic solids which may be used include calcium bentonite, kaolin, china clay, talc, perlite, mica, vermiculite, silicas, quartz powder, montmorillonite and mixtures thereof. Antifoam agents can include water dispersible liquids comprising polyorganic siloxanes like RHODOSIL® 416 (mixture of silicone-polyether block copolymer and free polyether available from Rhodia Inc., Cranbury, NJ). Dyes can include water dispersible liquid colorant compositions like PRO-IZED® Colorant Red (liquid seed colorant available from Gustafson LLC, Piano, TX). One skilled in the art will appreciate that this is a non-exhaustive list of formulation aids and that other recognized materials may be used depending on the propagating material to be coated and the synthetic mixture used in the coating.

Suitable examples of formulation aids include those listed herein and those listed in McCutcheon's 2001, Volume 2: Functional Materials, published by MC Publishing Company. The amount of formulation aids used may vary, but generally the weight of the formulation aids will be in the range of about 0.001 to 10000% of the propagating material weight, with the percentages above 100% being mainly used for pelleting small seed. For non-pelleted seed generally the amount of formulating aids is about 0.01 to 45% of the seed weight and typically about 0.1 to 15% of the seed weight. For propagating materials other than seeds, the amount of formulation aids generally is about 0.001 to 10% of the propagating material weight.

[150] Conventional methods of applying seed coatings can be used. Dusts or powders may be applied by tumbling the propagating material with a formulation comprising the synthetic mixture and a sticking agent to cause the dust or powder to adhere to the propagating material and not fall off during packaging or transportation. Dusts or powders can also be applied by adding the dust or powder directly to the tumbling bed of propagating materials, followed by spraying a carrier liquid onto the seed and drying. Dusts and powders comprising the synthetic mixture can also be applied by treating, for example, dipping at least a portion of the propagating material with a solvent such as water, optionally comprising a sticking agent, and dipping the treated portion into a supply of the dry dust or powder. This method can be particularly useful for coating stem cuttings. Propagating materials can also be dipped into formulations of wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water comprising the synthetic mixture, and then dried or directly planted in the growing medium. Propagating materials such as bulbs, tubers, corms and rhizomes typically need only a single coating layer to provide a biologically effective amount of the synthetic mixture.

[151] Propagating materials can also be coated by spraying a suspension concentrate directly into a tumbling bed of propagating materials and then drying the propagating materials. Alternatively, other formulation types like wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water may be sprayed on the propagating materials. This process is particularly useful for applying film coatings to seeds. Various coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al., Seed

Treatment: Progress and Prospects, 1994 BCPC Monograph No. 57 and the references listed therein. Three well-known techniques include the use of drum coaters, fluidized bed techniques and spouted beds.

Propagating materials such as seeds may be presized prior to coating. After coating the propagating materials are dried and then optionally sized by transfer to a sizing machine. These machines are known in the art for example, as a typical machine used when sizing corn (maize) seed in the industry.

[152] For coating seed, the seed and coating material are mixed in any variety of conventional seed coating apparatus. The rate of rolling and coating application depends upon the seed. For large oblong seeds such as those of cotton, a satisfactory seed coating apparatus comprises a rotating type pan with lifting vanes turned at sufficient rpm to maintain a rolling action of the seed, facilitating uniform coverage. For seed coating formulations applied as liquids, the seed coating must be applied over sufficient time to allow drying to minimize clumping of the seed. Using forced air or heated forced air can facilitate an increased rate of

application. One skilled in the art will also recognize that this process can be a batch or continuous process. A continuous process allows the seeds to flow continuously throughout the product run. New seeds enter the pan in a steady stream to replace coated seeds exiting the pan.

[153] The seed coating process of the present disclosure is not limited to thin film coating and may also include seed pelleting. The pelleting process typically increases the seed weight from 2 to 100 times and can be used to also improve the shape of the seed for use in mechanical seeders. Pelleting compositions generally contain a solid diluent, which is typically an insoluble particulate material, such as clay, ground limestone, powdered silica, etc., to provide bulk in addition to a binder such as an artificial polymer (e.g., polyvinyl alcohol, hydrolyzed polyvinyl acetates, polyvinyl methyl ether, polyvinyl methyl ether-maleic anhydride copolymer, and polyvinylpyrrolidinone) or natural polymer (e.g., alginates, karaya gum, jaguar gum, tragacanth gum, polysaccharide gum, mucilage). After sufficient layers have been built up, the coat is dried and the pellets graded. A method for producing pellets is described in Agrow, The Seed Treatment Market, Chapter 3, PJB Publications Ltd., 1994.

[154] Seed varieties and seeds with specific transgenic traits can be tested to determine which seed treatment options and application rates may complement such varieties and transgenic traits in order to increase rate of germination, increase rate of seedling emergence, increase rate of radicle growth, increase rate of early growth, increase pest control, increase disease control, increase plant height, increase vigor, increase resistance to abiotic environmental stress, and increase biomass and/or yield. Further, the good root establishment and early emergence that results from the proper use of the seed treatment comprising the synthetic mixture may result in more efficient nitrogen use, a better ability to withstand drought and an overall increase in yield potential.

[155] In another embodiment of the disclosure, the agricultural

composition is applied as a foliar formulation. Such formulations will generally include at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve as a carrier. The formulation ingredients are selected to be consistent with the physical properties of the synthetic mixture, mode of application and environmental factors such as soil type, moisture and temperature.

[156] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable

concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspoemulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.

[157] The general types of solid compositions are, for example, dusts, powders, granules, pellets, prills, pastilles, tablets and filled films (including seed coatings), which can be water-dispersible ("wettable") or

water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The synthetic mixture can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation comprising the synthetic mixture can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the synthetic mixture. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.

[158] Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry

formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other

subterranean plant parts and/or foliage through systemic uptake. Effective foliar formulations will typically contain from about 10^"3 M to 10^"11 M of the synthetic compounds. In other embodiments, formulations contain from about 10^"5 M to 10^"10 M of the synthetic compounds.

[159] In another embodiment of the disclosure, the agricultural

composition is applied to soil either prior to or following planting of plant propagating materials. Agricultural compositions can be applied as a soil drench of a liquid formulation, a granular formulation to the soil, a nursery box treatment or a dip of transplants. Of note is an agricultural

composition of the present disclosure is applied to the soil in the form of a soil drench liquid formulation. Other methods of contact include

application the agricultural composition by direct and residual sprays, aerial sprays, gels, seed coatings, microencapsulations, systemic uptake, foggers, fumigants, aerosols, dusts and others. One embodiment of a method of contact is a dimensionally stable fertilizer granule, stick or tablet comprising the synthetic compounds or synthetic mixture of the disclosure. Effective soil formulations will typically contain from about 10^"3 M to 10^"11 M of the synthetic compounds. In another embodiment, formulations contain from about 10^"5 M to 10^"10 M of the synthetic compounds.

[160] The methods of this disclosure is applicable to virtually all plant species. Seeds that can be treated include, for example, wheat (Triticum aestivum L), durum wheat (Triticum durum Desf.), barley (Hordeum vulgare L), oat (A vena sativa L), rye (Secale cereale L), maize (Zea mays L), sorghum (Sorghum vulgare Pers.), rice (Oryza sativa L), wild rice (Zizania aquatica L), millet (Eleusine coracana, Panicum miliaceum), cotton (Gossypium barbadense L. and G. hirsutum L), flax (Linum usitatissimum L), sunflower (Helianthus annuus L), soybean (Glycine max Merr.), garden bean (Phaseolus vulgaris L), lima bean (Phaseolus limensis Macf.), broad bean (Vicia faba L), garden pea (Pisum sativum L), peanut (Arachis hypogaea L), alfalfa (Medicago sativa L), beet (Beta vulgaris L), garden lettuce (Lactuca sativa L), rapeseed (Brassica rapa L. and B. napus L), cole crops such as cabbage, cauliflower and broccoli (Brassica oleracea L), turnip (Brassica rapa L), leaf (oriental) mustard (Brassica juncea Coss.), black mustard (Brassica nigra Koch), tomato (Lycopersicon esculentum Mill.), potato (Solanum tuberosum L), pepper (Capsicum frutescens L), eggplant (Solanum melongena L), tobacco (Nicotiana tabacum), cucumber (Cucumis sativus L), muskmelon

(Cucumis melo L), watermelon (Citrullus vulgaris Schrad.), squash (Curcurbita pepo L, C. moschata Duchesne, and C. maxima Duchesne.), carrot (Daucus carota L), zinnia (Zinnia elegans Jacq.), cosmos (e.g., Cosmos bipinnatus Cav.), chrysanthemum (Chrysanthemum spp.), sweet scabious (Scabiosa atropurpurea L), snapdragon (Antirrhinum majus L), gerbera (Gerbera jamesonii Bolus), babys-breath (Gypsophila paniculata L, G. repens L. and G. elegans Bieb.), statice (e.g., Limonium sinuatum Mill., L. sinense Kuntze.), blazing star (e.g., Liatris spicata Willd., L.

pycnostachya Michx., L. scariosa Willd.), lisianthus (e.g., Eustoma grandiflorum (Raf.) Shinn), yarrow (e.g., Achillea filipendulina Lam., A. millefolium L), marigold (e.g., Tagetes patula L, T. erecta L), pansy (e.g., Viola cornuta L, V. tricolor L), impatiens (e.g., Impatiens balsamina L.) petunia (Petunia spp.), geranium (Geranium spp.) and coleus (e.g., Solenostemon scutellarioides (L.) Codd). Not only seeds, but also rhizomes, tubers, bulbs or corms, including viable cuttings thereof, can be treated with the synthetic mixture from, for example, potato (Solanum tuberosum L), sweet potato (Ipomoea batatas L), yam (Dioscorea cayenensis Lam. and D. rotundata Poir.), garden onion (e.g., Allium cepa L), tulip (Tulipa spp.), gladiolus (Gladiolus spp.), lily (Lilium spp.), narcissus (Narcissus spp.), dahlia (e.g., Dahlia pinnata Cav.), iris (Iris germanica L. and other species), crocus (Crocus spp.), anemone

(Anemone spp.), hyacinth (Hyacinth spp.), grape-hyacinth (Muscari spp.), freesia (e.g., Freesia refracta Klatt., F. armstrongii \N ^'. Wats), ornamental onion (Allium spp.), wood-sorrel (Oxalis spp.), squill (Scilla peruviana L. and other species), cyclamen (Cyclamen persicum Mill, and other species), glory-of-the-snow (Chionodoxa luciliae Boiss. and other species), striped squill (Puschkinia scilloides Adams), calla lily (Zantedeschia aethiopica Spreng., Z. elliottiana Engler and other species), gloxinia (Sinnigia speciosa Benth. & Hook.) and tuberous begonia (Begonia tuberhybrida Voss.). Stem cuttings can be treated and include those from such plants as, for example, sugarcane (Saccharum officinarum L), carnation (Dianthus caryophyllus L), florists chrysanthemum

(Chrysanthemum mortifolium Ramat.), begonia (Begonia spp.), geranium (Geranium spp.), coleus (e.g., Solenostemon scutellarioides (L.) Codd) and poinsettia (Euphorbia pulcherrima Willd.). Leaf cuttings which can be treated with the synthetic mixture can include, for example, those from begonia (Begonia spp.), african-violet (e.g., Saintpaulia ionantha Wendl.) and sedum (Sedum spp.). The above recited cereal, vegetable,

ornamental (including flower) and fruit crops are illustrative, and should not be considered limiting in any way. For reasons of economic importance, other embodiments of this disclosure include wheat, rice, maize, barley, sorghum, oats, rye, millet, soybeans, peanuts, beans, rapeseed, canola, sunflower, sugar cane, potatoes, sweet potatoes, cassava, sugar beets, tomatoes, plantains and bananas, and alfalfa. [161] In any of the formulations and applications described above, one or more than one synthetic mixtures may be included. The disclosure also relates to a method of treating plant material. The method comprises; a) providing an agricultural composition comprising the

disclosed synthetic mixture; and

b) contacting plant material with the agricultural composition. Any number and combination of the disclosed synthetic mixtures may be included in the agricultural compositions described. Any of the above described methods can be used to contact the plant material with the agricultural composition, including, for example, contacting seeds, thereby forming a seed coating; contacting plant material through application of the agricultural composition to soil either prior to or following planting the plant propagating material.

[162] Although the foregoing disclosure has been described in some detail by way of illustration and example for purposes of clarity of understanding, certain changes and modifications may be practiced within the scope of the appended claims.

EXAMPLES

[163] It should be understood that these Examples, while demonstrating some embodiments of the disclosure, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications of the disclosure to adapt it to various uses and conditions.

[164] The meaning of abbreviations is as follows: "hr" means hour(s), "min" means minute(s), "L" means liter(s), "ml_" means milliliter(s), "μΙ_' means microliter(s), "mM" means millimolar, "M" means molar, "mmol" means millimoles, "g" means gram(s), "mg" means milligram(s), "ppm" means parts per million, "w/w" means weight/weight, "cSt" means centiStokes. "~" means approximately, "cm" means centimeter, "m" means meter(s), " ' " means inch(es), "Dl" means deionized, "V/V" means volume to volume. THF is tetrahydrofuran and DMF is dimethylformamide. [165] As used in the Examples below, THF (anhydrous 99.9%), DMF (anhydrous 99.8%), 1 -(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (98%), oxalyl chloride, palmitoleic acid,

dimethylaminopyridine, triethylamine and acetic anhydride were purchased from Sigma-Aldrich (Milwaukee, Wl) and were used as supplied. A fungicide mixture, 40.3% (by weight) of fludioxonil is available from

Syngenta Crop Protection, Inc., Greensboro, North Carolina.

[166] Palmitoleic acid chloride was prepared from palmitoleic acid via treatment with oxalyl chloride followed by distillation of the product. ¹H NMR spectra were recorded at 500 MHz Bruker machine. The proton chemical shifts are given in ppm relative to deuterated dimethyl sulfoxide (DMSO).

[167] The intermediates A, B and C were prepared as per the procedures disclosed in the US Patent No. 7,485,718.

Preparation of Dimer (A), Trimer (B) and Tetramer (C) amine derivatives

C

[168] The dimer amine (A) was synthesized via a multi-step synthesis described as shown in the scheme below. Glycosilation of separately prepared intermediates D and E provided protected

intermediate F. Sequential deprotection of protecting groups from this intermediate provided the dimer amine (A).

[169] The trimer amine (B) was synthesized by the glycosylation of the dimer intermediate G with the thiol ether derivative D to provide protected intermediate H. Sequential deprotection of protecting groups from this intermediate provided the trimer amine (B).

[170] The tetramer amine (C) was synthesized by the glycosylation of the trimer intermediate H with the thiol ether derivative D to provide protected intermediate J. Sequential deprotection of protecting groups from this intermediate provided the tetramer amine (B).

Example 1 : Synthesis of a synthetic mixture of Diqlucosamine Derivatives 2

[171] The mixture of diglucosamine derivatives include, but are not limited to:

[172] A two necked flask fitted with a septum and nitrogen inlet was charged with dimer-amine A (0.050 g, 0.1412 mmol) and DMF (1 mL).

The mixture was cooled to 0 ^°C and triethylamine (0.014 g, 0.141 mmol) was added, followed by addition of palmitoleic acid chloride (0.032 g,

0.127 mmol) at 0 ^°C. The mixture was warmed to RT and stirred overnight to obtain a white slurry. The mixture was cooled back from RT to 0 ^°C and

DMF (1 mL) and MeOH (0.1 mL) were added to the mixture. To the resulting mixture at 0 °C, triethylamine (0.0213 g, 0.212 mmol) was added followed by drop wise addition of acetic anhydride (0.0129 g, 0.127 mmol).

The mixture was warmed to RT and stirred overnight. The solvents were evaporated under high vacuum and the resulting solid was mixed well with cold water (3 mL) and filtered. The filtered product was washed with cold water (2 x 1 mL) and dried under vacuum to obtain a white solid (0.074 g) which is identified as diglucosamine derivative comprising N-linked

palmitoleic acid, including structures 2-1 and 2-2, as shown above

schematically.

[173] The ¹H NMR spectra (500 MHz, DMSO-D6) of the mixture

showed peaks corresponding N-COCI- (1 .85 -1 .92) and N-COC15H29

(0.89, 1 .26-1 .33, 1 .5, 2.0, 2.2, 5.4) groups indicative of the incorporation of acetyl and palmitoleic and groups. IR spectra indicate broad peaks at cm^"1 and 3290 cm^"1 indicative of amide functional groups. MALDI-TOF

spectral data confirmed products corresponding to possible palmitoleic

and acetyl amide structures: 655.4 (M + Na⁺ monopalmitoleic mono

acetamide), 849.6 (M + Na⁺ dipalmitoleic amide) and 461 .2 (M + Na⁺

diacetamide).

Example 2: Synthesis of a synthetic mixture of Triglucosamine

Derivatives 3

Mixture of

Glucosamine

Derivatives

[174] Using a similar procedure as described in Example 1 , a reaction of trimer amine B (0.050 g, 0.097 mmol) with palmitoleic acid chloride (0.025 g, 0.092 mmol) and triethylamine (0.0196 g, 0.194 mmol) followed by treatment with acetic anhydride (0.0093 g, 0.092 mmol) provided a white slurry. The slurry was dried and washed with water (2 x 1 mL) and dried under vacuum to obtain a white solid (0.053 g), which is identified as triglucosamine derivative comprising N-linked palmitoleic acid, including structures 3-1 , 3-2 and 3-3, as shown above schematically. ¹ H NMR spectra (500 MHz, DMSO-D6) showed multiple peaks corresponding N-COCh 0 -85 -1 .92) and N-COCi₅H₂₉ (0.89, 1 .26-1 .33, 1 .5, 2.0, 2.2, 5.4) groups indicative of the incorporation of acetyl and palmitoleic groups. IR spectra indicate broad peaks at 1665-1675 cm^"1 and 3290 cm^"1 indicative of amide functional groups. MALDI-TOF spectral data confirmed products corresponding to possible palmitoleic and acetyl amide structures: 858.5 (M + Na⁺ monopalmitoleic-di acetamide), 1052.7 (M + Na⁺ dipalmitoleic mono acetamide) and 664.3 (M + Na⁺ triacetamide).

Example 3: Synthesis of a synthetic mixture of

Tetraqlucosamine Derivatives 4

[175] Using a similar procedure as described in Example 1 , reaction of tetramermer amine C (0.050 g, 0.074 mmol) with palmitoleic acid chloride (0.019 g, 0.070 mmol) and triethylamine (0.0149 g, 0.147 mmol) followed by treatment with acetic anhydride (0.0071 g, 0.070 mmol) provided a white slurry. The slurry was dried and washed with water (2 x 1 ml_) and dried under vacuum to obtain a white solid (0.053 g), which is identified as tetraglucosamine derivative comprising N-linked palmitoleic acid, including structures 4-1 , 4-2, 4-3 and 4-4 as shown above

schematically. ¹ H NMR spectra (500 MHz, DMSO-D6) showed peaks corresponding N-COCH3 (1 .85 -1 .92) and N-COCi₅H₂₉ (0.89, 1 .26-1 .33, 1 .5, 2.0, 2.2, 5.4) groups indicative of the incorporation of acetyl and palmitoleic groups. IR spectra indicate broad peaks at 1680-1670 cm^"1 and 3300 cm^"1 indicative of amide functional groups. MALDI-TOF spectral data confirmed products corresponding to possible palmitoleic and acetyl amide structures: 1061 .6 (M + Na⁺ monopalmitoleic-tri acetamide), 1255.8 (M + Na⁺ dipalmitoleic di acetamide), 1465.9 (M + Na⁺ tripalmitoleic mono acetamide) and 867.4 (M + Na⁺ triacetamide).

Seed Germination Assay

[176] All materials, with the exception of the corn seeds were sterilized before use. An aqueous solution of the test compounds (25 ml_, 10^"7 M in Dl-water) was prepared for a set of five repeat experiments. A fungicide solution was added to each of the aqueous solutions of the test compounds. Five Petri dishes and 100 seeds were used to test one composition. Each corn seed was inspected for uniformity and lack of cracks in the seed prior to use. A piece of filter paper was used to cover the inner side of each Petri dish to allow uniform distribution of testing solution. Twenty corn seeds were placed on the filter paper area of one Petri dish. Each seed was placed on the filter paper with the flat side of the corn seed facing upwards. The seeds were placed on the filter paper so that the corn seeds were not touching each other. 5 ml_ of the test compound solution was carefully poured in the Petri dish. Control experiments were set up the same way with 20 seeds and 5 ml_ of deionized water per dish without any active species. The lid was placed on the Petri dish and was sealed with Para-film. Five dishes with repeat experiments were stacked. Each stack of dishes was wrapped twice with aluminum foil to prevent the seeds receiving any light and the stacks were germinated in dark at the ambient laboratory conditions. The stacks were inspected after 16, 24, 40, 48 and 64 h. The number of germinated seeds was counted and the percent of germination on each dish was calculated. Radicle emergence was used as the germination indicator. The dishes were placed unwrapped at room temperature for one day and the number of germinated seeds was counted to assure seeds were able to germinate and difference in germination yields were not caused by bad seed quality. Statistical analyses were performed by calculating the standard deviation of the five repetitions for each experiment. The data was deemed acceptable when the standard deviation was less than 10%.

[177] Once seeds from seed germination assay have reached 60- 70% germination, the plates were left under light to grow. After 1 day under light the seeds were separated based upon the length of radicle. The radicle length was measured and the percentage of germinating seed with radicle length of greater than 1 .5 cm was determined.

Example 4: Germination Testing of Corn Seeds treated with the

Compositions of Examples 1-3

[178] Corn seeds treated with the compositions of examples 1 -3 were evaluated using the seed germination assay previously described. The results are summarized in Table 1 .

TABLE 1

[179] Corn seeds treated with Example 1 showed similar percent germination when compared to the control. Corn seeds treated with composition of Example 2 showed higher % germination than untreated control particularly at early stage of germination (16, 24, 40 and 48 h). Corn seeds treated with the mixture of Example 3, showed a greater percent germination at 16 and 24 hours. Corn seeds treated with

Examples 1 , 2 or 3 all demonstrated a greater percentage of seeds with radicle length longer than 1 .5 cm than did the control sample. The results were deemed statistically significant when the standard deviations (indicated in brackets) of the averages do not overlap.

Claims

What is claimed is: . A process comprising;

wherein XR³ is an azide; or X is O or S and R³ is H, Ci to C6 alkyl or aryl;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-; each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C2 to C12 alkenyl, or C2 to C12 alkynyl; each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹, -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO₂, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to C6 alkyl, aryl, or aralkyl; G is O or S; and

Z is -OH, halogen, methoxy or ethoxy;

in the presence of a base or a carboxylic acid activator; and

2. The process of claim 1 wherein the acylating agent of step 2) is an acid halide.

3. The process of claim 1 or 2 wherein the second acylating agent is acetic anhydride.

4. The process of claim 2 wherein the acid halide is palmitoleic acid chloride.

5. The process of any one of claims 1 , 2, 3 or 4 wherein the ratio of the number of moles of the acylating agent to the number of moles of amine in the one or more compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 .

6. A synthetic mixture formed by the process of any one of claims 1 , 2, 3, 4 or 5.

7. A process comprising;

1 ) providing one or more compounds having a structure

according to A, B and/or C in a liquid carrier;

R²-NCG

wherein XR³ is an azide; or X is O or S and R³ is H, Ci to C6 alkyl or aryl;

each R⁴ is independently arylene, heteroarylene comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkylene, C2 to C12

alkenylene or C₂ to C12 alkynylene;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹, -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO₂, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyi; G is O or S; 3) optionally contacting any remaining amine with a second acylating agent; or optionally contacting any remaining amines with a Ci to Ce isocyanate compound.

8. The process of claim 7 wherein the second acylating agent is

acetic anhydride.

9. The process of claim 7 or 8 wherein the ratio of the number of moles of isocyanate to the number of moles of amine in the one or more compounds A, B and/or C is in the range of from 0.5:1 to 1 .5:1 .

10. A synthetic mixture comprising two or more compounds, wherein each of the two or more compounds comprises a non-reducing glucose unit, a reducing glucose unit, and at least one N-linked substituent -AR²:

(1 -1 ).

a compound having a structure (1 -2), wherein the at least N-linked substituent -AR² is at the reducing glucose unit:

(1 -2),

(1 -3), or

d. a compound having a structure (1 -4), wherein the at least one N-linked substituent -AR² is at a glucose unit penultimate to the reducing glucose unit:

(1 -4),

wherein m = 0 or 1 ; n = 0 or 1 ;

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹ )₂, -C_qF_2q+i , -OC_qF_2q+i , -NO2, -N₃, -OR¹ , SR¹ , N(R¹ )₂, and Ci to C₆ alkyl; q is 1 to 6; each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl; and wherein structures (1 -1 ), (1 -2), (1 -3) and (1 -4) are different from each other.

1 1 . The synthetic mixture of Claim 10, wherein m = 0 and n = 0,

comprising:

(2-1 ), and

a compound having a structure (2-2), wherein the at least N-linked substituent -AR² is at the reducin glucose unit:

(2-2)

each R¹ is independently H, Ci to C6 alkyl, aryl, or aralkyl;

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁶ is independently H, aryl, heteroaryl comprising 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulfur, Ci to C12 alkyl, C2 to C12 alkenyl, or C2 to C12 alkynyl; each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i, -OC_qF_2q+i , -NO₂, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to C6 alkyl, aryl, or aralkyi; and wherein the structures (2-1 ) and (2-2) are different from each other.

12. The synthetic mixture of Claim 10, wherein m = 1 and n=0,

comprising two or more of:

a. a compound having a structure (3-1 ), wherein the at least one N-linked substituent -AR² is at the non-reducing glucose unit:

(3-1 )

(3-2), or

(3-3), and

each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyi;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

each R⁴ and R⁶ is optionally substituted by 1 to 2 substituents chosen independently from halogen, -CN, -C(O)OR¹ , -C(O)N(R¹)₂, -C_qF_2q+i , -OC_qF_2q+i , -NO2, -N₃, -OR¹ , SR¹ , N(R¹)₂, and Ci to C₆ alkyl; q is 1 to 6;

each R¹ is independently H, Ci to C₆ alkyl, aryl, or aralkyi; and wherein the structures (3-1 ), (3-2) and (3-3) are different from each other.

The synthetic mixture of Claim 10, wherein m=1 and n=1 , comprising two or more of:

a. a compound having a structure (4-1 ), wherein the at least one N-linked substituent -AR² is at the non- reducing glucose unit:

(4-1 )

b. a compound having a structure (4-2), wherein the at least one N-linked substituent -AR² is at the reducing glucose unit:

(4-2)

c. a compound having a structure (4-3), wherein the at least one N-linked substituent -AR² is at the glucose unit penultimate to the non-reducing glucose unit:

(4-3), or

d. a compound having a structure (4-4), wherein the at least one N-linked substituent -AR² is at the glucose unit enultimate to the reducing glucose unit:

(4-4)

A is -C(O)-, -C(S)-, -C(S)NH-, -C(O)NH-, -C(O)O- or C(O)S-;

each Y¹ is independently H, -AR¹ or -AR²; each R¹ is independently H, Ci to Ce alkyl, aryl, or aralkyl;

each R² is independently C12 to C22 alkyl, C12 to C22 alkenyl, C12 to

C₂₂ alkynyl or -R⁴-R⁵-R⁶;

each R⁵ is independently -O-, -S-, -N(R¹)- or -NHC(O)-;

14. The synthetic mixture of claim 10 wherein the synthetic mixture comprises at least one of structure (1 -1 ) and at least one of structure (1 -2).

15. An agricultural composition comprising an aqueous solution of the synthetic mixture of any one of claims 10, 1 1 , 12, 13 or 14.

16. The agricultural composition of claim 15 further comprising

insecticides, fungicides, nematocides, bactericides, acaricides, entomopathogenic bacteria, viruses, fungi, microorganisms, growth regulators, signal compounds or a combination thereof.

17. The agricultural composition of claim 16 comprising a growth

regulator selected from rooting stimulants, chemosterilants, repellents, attractants, pheromones, feeding stimulants or combinations thereof.

18. The agricultural composition of claim 16 comprising a signal

compound selected from apocarotenoids, flavonoids, jasmonates, strigolactones or combinations thereof.

19. A method of treating a propagule comprising steps:

a) providing the agricultural composition of claim 15; and

b) contacting the propagule with the agricultural composition.

20. The method of claim 19 wherein the propagule of step b) is a seed thereby forming a seed coating.

21 . The method of claim 19 wherein b) contacting the propagule with the agricultural composition comprises contacting the propagule with the agricultural composition through application of the agricultural composition to soil either prior to or following planting the propagule.

22. The method of any one of claims 19, 20 or 21 wherein the

agricultural composition of step (a) further comprises one or more of: insecticides, fungicides, nematocides, bactericides, acaricides, entomopathogenic bacteria, viruses, fungi, microorganisms, growth regulators, and signal compounds.

23. The method of claim 22 wherein the growth regulator is one or more of rooting stimulants, chemosterilants, repellents, attractants, pheromones, feeding stimulants, and combinations thereof.

24. The method of claim 22 wherein the signal compound one or more of apocarotenoids, flavonoids, jasmonates, strigolactones, and combinations thereof.

25. A plant seed coated with the agricultural composition of claim 15.

26. The plant seed of claim 25 wherein the agricultural composition comprises an insecticide, a fungicide, a nematicide and a biological agent.

27. The plant seed of claim 25 or 26 wherein the plant seed is a corn seed, a soybean seed or a wheat seed.

28. The plant seed of any one of claims 25 to 27 wherein the resulting plant expresses an insect resistant trait.

29. The plant seed of claim 28 wherein the insect resistant trait is due to the expression of a Bt protein.